Académique Documents
Professionnel Documents
Culture Documents
DEOlLlNG MANUAL
Revision 1.1
Author:
A. C. Lawrence, EPDi421
This dociinient I S confidential Neither the whole nor any part of this document m a y he ilisclosed to any third party without the !mor written consent of Shell Internationale Petroleum Maatschappij B.V., The Hague. the Netherlands. The copyright of this docuiiieiit is vested in Shell lriteriiationale Petroleum blaatschappi] B V.. The Hague. the Netherlands All rlyhts reserved. Neither the whole nor any pan of this docuinent m a y he reproduced, stored in airy retrieval systciii ot traiisniitled In aiiy form or hy any means (electronic, mechanical. reprographic. recording or otherwise) withoot the prior writlnri consent of the copyright owner
Revision history
REVISION HISTORY
Revision
Draft
Issue date
_____
By
Revision details
First draft of revised manual. Developed from existing SIPM DehydratiodDeoiling Manual EP 89-1 50. Update based on literature searches of SlPM EP report database, in-house files, OWTC test work and a questionnaire circulated to operating companies. Diagrams not included. Updated based on comments received on the Draft. Significant changes included the inclusion of all diagrams, a section introducing sludge treatment, clarification of iso-kinetic and isoenergetic sampling, inclusion of tables summarising the performance of equipment in tests, trials and operating installations and an appendix summarising the equations used to predict hydrocyclone performance. Updated with remaining comments received from Revision 1.O issue. Equations in Appendix A and B corrected. Sizing of sampling quill added to Appendix B. Section 7 updated. Results from Galai trial included.
Revision 1 .O
Revision 1.1
S Nov 1993
Corrections
Forward to: SIPM, Posthus 162, 2501 AN Dcn Haag, The Netherlands - Attention EPD/42
Itrp, ii
SIPM Deoiliiig M ~ i i i i i dEP , 93-1335. Rev 1.1, Nov 1993, File iiamr = 0TITLE.DOC
Table of contents
INTRODUCTION
1.1. 1.2. 1.3. 1.4. 1.5. 1.6. 1.7. 1.8.
................................................................................................................
1-1
1-1 1-1 1-1 1-1 1-2 1-3 1-3 1-3
................................................................................................................... ORDER OF DOCUMENT PRECEDENCE............................................................................ STRUCTURE OF DEOlLlNG MANUAL............................................................................... INFORMATION BASE......................................................................................................... EQUIPMENT BRANDS AND SUPPLIERS........................................................................... ABBREVIATIONS ...............................................................................................................
DISTRIBUTION
.....................................................................
2-1
2-1
2-1 2-1 2-2 2-2 2-3 2-3 2-5 2-5 2-6 2-6 2-7 2-7 2-7 2-7 2-8
...........................................................................................................................
Produced water ...................................................................................................... Ballast water .......................................................................................................... Process water ........................................................................................................ Drainage water ...................................................................................................... Other waters ..........................................................................................................
2-1
2.3.
Hydrocarbons derived from production streams ..................................................... Treatment chemicals.............................................................................................. Suspended solids ................................................................................................... Heavy metals ......................................................................................................... Salinity .................................................................................................................. pH ......................................................................................................................... Hardness ............................................................................................................... Thermal contamination .......................................................................................... Dissolved oxygen ................................................................................................... Organic carbon ......................................................................................................
2-3
2.4.
.......................................................................................
2-8
EMULSIONS
3.1.
......................................................................................................................
General................................................................................... Distribution of phases ............................................................... Stability ............................................................................................. Size distributions................................................................
3-1
3-1 3-1
DEFINITIONS......................................................................................................................
3.1 .1. 3.1 .2. 3.1 .3. 3.1.4.
........................ ......................
3-1
3.2.
3-2 3-2
3-2
3.3.
STABlLlSATlON OF EMULSIONS......................................................................................
3-2
3-2 3-2
SlPM Dcoiliiig
Miiniiiil.
itioiic
= Ollll~I~.DOC
P q e iii
Table of contents
3.3.3. 3.3.4. 3.3.5. Interfacial tension ................................................................................................... Contact angles and wetting of solids....................................................................... Emulsion stabilisers ............................................................................................... General .................................................................................................................. Emulsion breaking chemicals ................................................................................. Other methods of emulsion treatment ..................................................................... 3-3 3-3 3-4
3.4.
3-6
4 . WATER DISPOSAL
4.1. 4.2.
..........................................................................................................
.........................................................................................................
4-1
4-1
4.3.
General .................................................................................................................. Water compatibility ................................................................................................ Permeability impairment......................................................................................... Secondary waste water streams .............................................................................
4-3
4.4.
4.5.
4-6
5-1
GENERAL ........................................................................................................................... 5-1 SAMPLE POINTS 5.2.1. Location of sampling points ....................................................................................
5.2.2. 5.2.3.
................................................................................................................
Orientation of sampling points ................................................................................ 5-2 Design of sampling quills........................................................................................ 5-2 Materials ................................................................................................................ 5-3 Cleaning of sample containers................................................................................ 5-4
5-1
5-1
5.3.
SAMPLE CONTAINERS......................................................................................................
5.3.1. 5.3.2.
5-3
5.4. 5.5.
5-4 5-5
Introduction............................................................................................................ 5-5 lsokinetic conditions ............................................................................................... 5-5 Procedure for routine sampling............................................................................... 5-6
5.6.
Introduction............................................................................................................ 5-6 Sampling procedure to determine droplet size distribution....................................... 5-7 Effect of process pressure on sampling and droplet size distributions ..................... 5-7
............................................
5-6
5.7.
Introduction............................................................................................................ 5-8 Chemical Preservation ........................................................................................... 5-9 Sample storage ...................................................................................................... 5-9
.......................................................................
5-8
P ( q y iv
SlPM Droilinfi Miiituril. EP 93.1315. Rev 1.1. Nriv 1993. File niime = 0TITLE.DOC
Table o f contents
6
.............................................................................................
~1
6-1
Introduction............................................................................................................ Sample preparation................................................................................................ Hydrocarbon extraction .......................................................................................... Removal of polar.compounds................................................................................. Infrared analysis .................................................................................................... Dispersed and dissolved hydrocarbons .................................................................. Gravimetric analysis .............................................................................................. Visible spectrum colourimetry ................................................................................ Gas chromatography ............................................................................................. Others ................................................................................................................... General..................................................................................................................
6-1 6-2 6-2 6-3 6-3 6-5 6-5 6-6 6-6 6-6
6-1
6.3.
HYDROCARBONS.OTHER METHODS
6.3.1 . 6.3.2. 6.3.3. 6.3.4. 6.3.5.
.............................................................................
6-5
6.4. 6.5.
..............................................................................
6-7
6-7
General.................................................................................................................. 6-8 6-8 Sampling ............................................................................................................... Potential problems in measuring droplet size distributions...................................... 6-8 Droplet size distribution analysers .......................................................................... 6-8 Particle size analyser trials ................................................................................... 6-10
....................................................
6-8
...............................................
7-1
7-1
7-1 7-1 7-2 7-2 7-3 7-3 7-3 7-4 7-5 7-5 7-7 7-7 7-7 7-8 7-8 7-8 7-8 7-8
7.2.1. 7.2.2. 7.2.3. 7.2.4. 7.2.5. 7.2.6. 7.2.7. 7.2.8. 7.2.9. 7.2.10.
Introduction...................................................................................................................... Sources and magnitude of water streams (1) .................................................................... Identify contaminants in the waste water stream (2) .......................................................... Identify treated water quality requirements (3) ................................................................... Select a suitable process location for the water treatment system (4) ................................ Identify upstream methods of improving ease of water treatment (5)................................. Select the number of treatment stages (6) ........................................................................ Select the suitable deoiling equipment (7) ......................................................................... Treatment or disposal of secondary streams (8) ............................................................... System optimisation and integration (9) ............................................................................
7-1
7.3.
Introduction...................................................................................................................... Maximising droplet size .................................................................................................... Minimising the hydrocarbon content in the feed stream ..................................................... Production separators ...................................................................................................... Stable feed streams .......................................................................................................... Recycle streams ............................................................................................................... Mixing of water streams .................................................................................................... Treatment chemicals ........................................................................................................
..................................
7-7
7.4.
7 . 5 .
7.6.
8. DISPERSED HYDROCARBONS
8.1.
8.1 .1. 8.1.2.
....................................................................................
8-1-1
INTRODUCTION ..............................................................................................................
8-1-1 Scope of chapter ................................................................................................. 8-1-1 Equipment for dispersed hydrocarbons .Summary tables ................................... 8-1-1
Table of contents
8.2. 8.3. DEFINITIONS..................................................................................................................
8.2.1. Deoiling efficiencies............................................................................................
..
8-2-1
8-2-1
COALESCERS
8.3.1. 8.3.2. 8.3.3. 8.3.4. 8.3.5. 8.4.1. 8.4.2. 8.4.3.
General .............................................................................................................. Definitions .......................................................................................................... Performance variables........................................................................................ Installation/Configuration.................................................................................... Coalescer designs .............................................................................................. General .............................................................................................................. Floc separation .................................................................................................. Operation considerations.................................................................................... Introduction ........................................................................................................ performance variables........................................................................................ Installation/Configuration.................................................................................... Design guidelines ............................................................................................... Control configuration ..........................................................................................
................................................................................................................
8-3-1
8.4.
FLOCCULATION.............................................................................................................
8-4-1
8.5.
8-5-1
8.6.
DISCHARGE CAISSONS.................................................................................................
Introduction ........................................................................................................ Design guidelines ............................................................................................... Caisson internals................................................................................................ Operational considerations................................................................................. Introduction........................................................................................................ Performance variables........................................................................................ Installation/Configuration.................................................................................... Design guidelines ...............................................................................................
8-6-1
8.7.
API SEPARATOR
8.7.1. 8.7.2. 8.7.3. 8.7.4.
............................................................................................................
8-7-1
8.8.
8-8-1 8-8-1 8-8-3 8-8-4 8-8-5 8-9-1 8-9-1 8-9-1 8-9-8 8-9-9 8-9-11 8-10-1 8-10-1 8-10-1 8-10-5 8-10-6 8-10-7 8-10-7
8-8-1
8.9.
STATIC HYDROCYCLONE..............................................................................................
8.9.1. 8.9.2. 8.9.3. 8.9.4. 8.9.5. 8.9.6.
Introduction........................................................................................................ Definitions.......................................................................................................... Performance variables........................................................................................ InstallationlConfiguration.................................................................................... Control configuration.......................................................................................... Operational considerations ................................................................................
8-9-1
8-12-1
Ptrxc
vi
Table of contents
8.12.2. 8.1 2.3. 8.1 2.4. 8.12.5. 8.12.6. 8.13.1. 8.13.2. 8.13.3. 8.13.4. 8.13.5. Performance variables ...................................................... :............................... Installation/Configuration.................................................................................. Design guidelines .............................................................................................. Control configurations ....................................................................................... Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines .............................................................................................. Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines .............................................................................................. Control configuration......................................................................................... Operational considerations................................................................................ Crushed nut shell deep bed media filters ........................................................... Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration.................................................................................. Design guidelines.............................................................................................. 8-12-3 8-12-6 8-12-7 8-12-7 8-12-8 8-13-1 8-13-2 8-13-4 8-13-5 8-13-5 8-14-1 8-14-2 8-14-5 8-14-6 8-14-6 8-14-6 8-14-7 8-15-1 8-15-1 8-15-1 8-15-2 8-16-1 8-16-1 8-16-2 8-16-2 8-16-2 8-17-1 8-17-2 8-17-3 8-17-3
......................................................................................
8-13-1
....................................................................................
&-14-1
8-15-1
Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines.............................................................................................. Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Membrane trials ................................................................................................
8-16-1
8.17. MEMBRANES
8.1 7.1 . 8.1 7.2. 8.1 7.3. 8.1 7.4.
................................................................................................................
8-17-1
9. DISSOLVED HYDROCARBONS
9.1. 9.2. 9.3. INTRODUCTION
....................................................................................
9-1-1
9-1-1 9-2-1
9-3-1 9-3-2 9-3-3 9-3-4 9-4-1 9-4-1 9-4-2 9-4-2 9-5-1 9-5-1 9-5-3 9-5-4 9-5-4
..............................................................................................................
9-3-1
9.4.
9-4-1
9.5.
BIOLOGICAL TREATMENT.............................................................................................
9.5.1. 9.5.2. 9.5.3. 9.5.4. 9.5.5.
Introduction......................................................................................................... Aerobic processes............................................................................................... Anaerobic processes........................................................................................... Performance variables ........................................................................................ Installation/Configuration ....................................................................................
9-5-1
SlPM Dtwilittg Mntlurtl El' 93.1315 Rev 1.1. Nov IY93 File
ititiw
= 0TITLE.DOC
P u p vi;
Table o f contents
9.6.
ACTIVATED CARBON 9.6.1. Introduction........................................................................................................ 9.6.2. Performance variables........................................................................................ .................................................................................... 9.6.3. Installation/Configuration SOLVENT EXTRACTION 9.7.1. Introduction ........................................................................................................ 9.7.2. Co-current extraction..........................................................................................
~~~
....................................................................................................
9.7.
.................................................................................................
10 NEW TECHNOLOGY
~~
......................................................................................................
10-1
10-1
10-1
10-1
0-1
10.5. PERVAPORATION.............................................................................................................
........................................................
10-2
Appendix A
A.l.
A-I
A-1
A.2.
....................................................................
A-3
...............................................................
8-1
B-1 B-1 8-2 8-5 B-6
....................................................................................................................... Calculation of the mixing intensity in the process line ................................................... Pressure drop in the sampling system ............................................................................ Sizing the sample quill for isokinetic conditions ............................................................ Contrast with iso-kinetic sampling ..................................................................................
.......................................................
C-1
C-1 C-2
Appendix
D.l Oil-In-Water Monitor Testing .Phase I D.l .1. General ................................................................................................................. D.1.2. Monitors tested...................................................................................................... D.1.3. Variables investigated ........................................................................................... D.1.4. Summary of results ...............................................................................................
I u ~ : cv i i i
D .Oil-in-water
...............................................................................
................................................................................
D.1
D-1 D-1 D-1 D-2
D-1
Table o f contents
D.2 Oil-In-Water Monitor Testing .Phase It D.2.1. General................................................................................................................. D.2.2. Monitors tested ..................................................................................................... D.2.3. Variables investigated ........................................................................................... D.2.4. Summary of results ............................................................................................... D.3 Oil-In-Water Monitor Testing .Phase 111
...............................................................................
..............................................................................
............................................................................
E-1
E-1
E-1 E-1 E-1 E-1
OWTC particle size analyser trials E.l.l. General.................................................................................................................. E.1.2. Analysers tested .................................................................................................... E.1.3. Variables investigated ............................................................................................ E.1.4. Summary of results ................................................................................................ Galai CIS-1000 trials at KSLA E.2.1. Results of trial ........................................................................................................ E.2.2. Conclusions ...........................................................................................................
....................................................................................
E.2.
............................................................................................
........................................................................................................
F-1
F-1 F-2 F-2 F-2 F-2 F-2 F-2
...........................................................................................................................
Variables In Stokes Law .................................................................................................... F.2.1 Droplet size ............................................................................................................ F.2.2 Gravitational acceleration....................................................................................... F.2.3 Viscosity ................................................................................................................ F.2.4 Density difference .................................................................................................. The Effect Of Temperature On Stokes Law
F.3.
......................................................................
G-1
G-1 G-1 G-1 G-1 G-2 G-2 G-2 G-2 G-2 G-2 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-4
G.3. G.4.
........................................................................................
Hydrocyclone coalescer G.4.1 Description ........................................................................................................... G.4.2 Packaging............................................................................................................. G.4.3 Performance......................................................................................................... MPE SP Pack G.5.1 Description ........................................................................................................... G.5.2 Packaging............................................................................................................. G.5.3 Performance......................................................................................................... Monosep Spiralsep Coalescer ......................................................................................... G.6.1 Description ........................................................................................................... G.6.2 Packaging............................................................................................................. G.6.3 Performance......................................................................................................... Sulzer Mellapak G.7.1 Description ........................................................................................................... (3.7.2 Packaging ............................................................................................................. G.7.3 Performance......................................................................................................... Upflow Filter/Coalescers
...................................................................................................
G.5.
.....................................................................................................................
G.6.
G.7.
.................................................................................................................
G.8.
..................................................................................................
Table of contents
G.9.
................................................................................... G.10. Skimovex lnverto Filter/Coalescer ................................................................................... G.11. Elf Anvar Filter/Coalescer ................................................................................................. G.12. Plate interceptors.............................................................................................................. G.13. Natco Performax ...............................................................................................................
Expandable fibrous bed coalescer
.............................................................................................
H-1
H-1 H-1 H-2 H-2 H-3 H-4
....................................................................................................................... Reynolds number .............................................................................................................. Plate pack dimensions for droplet interception ..............................................................
............................................................................................................ Effect of Reynolds number ............................................................................................... Standard Shell CPI design ................................................................................................
Sizing a plate pack
............................................................
1-1 1-1 1-1
1-1 1-2 1-2
1-1
........................................................................................................................... Cut size diameter ................................................................................................................... Cut size diameter correlations ..............................................................................................
1.3.1 1.3.2 1.3.3 Equilibrium orbit theory .......................................................................................... Residence time model ............................................................................................ Empirical model .....................................................................................................
............................................................................................................. Empirical migration probability correlations ....................................................................... Empirical pressure drop correlations ................................................................................... Application of correlations to hydrocyclone trials ...............................................................
1.7.1 1.7.2 North Cormorant trials ............................................................................................ OWTC trials ...........................................................................................................
1 . 8 Nomenclature
........................................................................................................................
1-4
................................................
J-1
J-1 J-1 J-2 5-3
........................................................................................................................ Theory ................................................................................................................................. Comparison with experimental and field results ..............................................................
Parameters affecting solubility
.........................................................................................
K-1
K-1
K-1
Table o f contents
K.3. Results
..............................................................................................................................
K-2
...............................................................................................
1-1
1-1
1-1 1-2 1-2
....................................................................................................................... Alcoa Petrolox ................................................................................................................... SDI Extran .......................................................................................................................... X-Flow ................................................................................................................................ .. Stork-Wafilin ...................................................................................................................... Schelde-Delta ..................................................................................................................... WL Gore .............................................................................................................................
Hoogovens......................................................................................................................... Zenon .................................................................................................................................
1-2
1-2 1-2 1-2
1-3
Bibliography
.......................................................................................................
Bibliography-1
Bibliography-1 Bibliography-1 Bibliography-1
. 2. 3.
1
Introduction
Table of contents
Puge xi;
SlPM Deoi/iri# Marivol, EP 93-1315, Rev 1.1, Nov 1993, File nume = 0TlTLE.DOC
1. Introduction
1.1.
GENERAL
The production of hydrocarbons is usually associated with the generation of a waste water stream which requires treatment to allow it to be disposed in a safe and environmentally acceptable manner. Over the four years since the last revision of this manual both the technical aspects of waste water treatment and the philosophies governing waste water treatment have undergone significant changes, especially in the light of increasing environmental awareness in the community and in industry. New information and developments that have been incorporated into this update of the Deoiling Manual include; The use of droplet size distribution as tool in optimising the design and operation of waste water treatment equipment. The results of independent equipment testing programs conducted at the Orkney Water Test Centre. Procedures for the sampling of oil-in-water dispersions. The use of more advanced deoiling equipment such as hydrocyclones and centrifuges. New waste water treatment technologies under development. The removal of dissolved hydrocarbons.
1.2.
PURPOSE OF MANUAL
This updated Deoiling Manual has been designed to satisfy the following major objectives. To provide background information on all aspects of water deoiling including water sampling, analysis and characterisation, hydrocarbon-in-water emulsions and the disposal of treated water. To provide users with an understanding of the design principles and performance characteristics of currently available equipment for the removal of dispersed and dissolved hydrocarbons. To provide guidelines for deoiling equipment selection and facilities design. To provide a listing of reports, documents, papers and equipment trials relevant to the selection, testing or operation of deoiling equipment.
It should be emphasised that this Deoiling Manual should not be considered to be a fixed set of rules or methods governing deoiling and associated topics. It should serve as an introduction and a foundation to these subjects, but not hinder further developments and advancements.
1.3.
DlSTRIB UTlON
Unless otherwise authorised by SIPM, the distribution of this document is confined to companies forming part of the Royal Dutch/Shell Group or managed by a Group company, and to contractors nominated by them.
1.4.
1. Introduction
Deoiling Manual (This document) Dehydration Manual Addressing the removal of hydrocarbons and other contaminants from water streams. Addressing the removal of water from hydrocarbon streams.
However, until the new Dehydration Manual is completed, this document (Deoiling Manual) will coexist with the current Dehydration/Deoiling manual. In general, the order of document precedence should be as follows; This document (Deoiling Manual) should be used for all information relevant to deoiling. The current Dehydration/Deoiling manual (EP 89-0150) should be used for information specific to dehydration. In the event of conflict, this document (Deoiling Manual) shall take precedence.
1.5.
Introduction - Forms the preamble to the Deoiling Manual, outlining the objectives, scope and organisation of the document. Characterisation of waste water Discusses the elements defining the character of waste waters such as the source of the waste water, typical contaminants, the distribution and nature of contaminants and measurements of water quality. Emulsions Discusses the characteristics, formation, stability and treatment of hydrocarbon in water emulsions. Water disposal Discusses the technical and environmental considerations governing the methods of water disposal, including both surface and subsurface disposal. Waste water sampling - Discusses the sampling procedures required to obtain representative samples of waste water, particularly for water containing dispersed hydrocarbon droplets. Waste water analysis Discusses the analysis methods required to determine the hydrocarbon content in waste waters, the measurement of dispersed and dissolved hydrocarbons, the performance of on-line oil-in-water analysers and the measurement of dispersed droplet size distributions. System design and integration Discusses the selection and application of deoiling equipment with emphasis on system integration. This approach recognises that the deoiling equipment forms only one part of the production process and must be integrated with other systems. Topics covered include the location of the deoiling equipment in the process train, the minimisation of emulsifying forces, the influence of direct and indirect addition of treatment chemicals on the deoiling process and the integration of recycling hydrocarbon reject streams into the process. Deoiling equipment Dispersed hydrocarbons Examines proven deoiling equipment in detail. Information provided includes design principles, process design requirements, deoiling performance, typical unit dimensions and weights and basic sizing guidelines. Where applicable, tables are given summarising the performance of the equipment in a range of Shell installations, pilot plant tests and field trials. Deoiling equipment Dissolved hydrocarbons Examines the range of processes available for the removal of dissolved hydrocarbons from water streams. New technology Briefly discusses a selection of new technologies currently under development for the treatment of waste waters.
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Appendices
The Appendices cover a wide range of topics which cannot be easily incorporated into the text of the manual, particularly calculation methods such as mixing intensity calculations, plate pack sizing and methods for predicting the levels of dissolved hydrocarbons in
Pu'qe 1-2
SlPM Droilinji Mnnud, EP 93-1315. Rev 1.1. Nov 1993, File ncrmc = IINTRO.DOC
I . Introduction
Bibliography The Bibliography lists all the references used for the compilation of this Deoiling Manual. If not available through local sources, these references can be requested from the SlPM Report Library EPD/52 or through SlPM EPD/4.
water.
1.6.
INFORMATION BASE
The starting point for this Deoiling Manual has been the 1989 SlPM Dehydration/Deoiling Manual (EP 89-0150). The deoiling sections of EP 89-0150 are now superseded by this updated Deoiling Manual. The additional information incorporated into this update of the Deoiling Manual has been taken from the following sources. i) ii) Literature survey of the SlPM STAIRS document database for reports related to deoiling and associated topics. Details of the keyword searches conducted are included in the Bibliography. Input from operating companies including; Requests for relevant references and documentation. Requests for comments on the existing Dehydration/Deoilingmanual. A questionnaire to identify the performance of existing deoiling equipment installations. iii) iv) Results of test work conducted at the Orkney Water Test Centre and experimental work conducted at KSLA. Discussions with equipment vendors.
1.7.
1.8.
ABBREVIATIONS
The following abbreviations have been used in the Deoiling Manual. AMS APHA API ASTM BOD BTEX C-H CCD COD CPI DC DAF DGF DOC E&P EPA GBS GOR HSE IGF IP IR Amsterdam Method Series (Analytical methods developed and documented by KSLA) American Public Health Association American Petroleum Institute American Society for Testing and Materials Biological Oxygen Demand Benzene, Toluene, Ethyl benzene, Xylene Carbon-Hydrogen Charge Coupled Device Chemical Oxygen Demand Corrugated Plate Interceptor Dissolved Carbon Dissolved Air Flotation Dissolved Gas Flotation Dissolved Organic Carbon Exploration and Production Environmental Protection Authority (USA) Gravity Based Storage Gas to Oil Ratio Health, Safety and Environmental Induced Gas Flotation Institute of Petroleum Infrared
SlPM Dcnilinx Moniiol. EP 93-1315. Rev 1.1, Nov 1993. File IKUW = IINTR0.DOC
Puxe 1-3
1. Introduction
ISF IS0 KSEPL
Induced Static Flotation International Organisation for Standardisation Royal Dutch/Shell Exploration and Production Laboratory Royal Dutch/Shell Laboratories Amsterdam Membrane Like Material Orkney Water Test Centre Parallel Plate Interceptor Shell lnternationale Petroleum Maatschappij B.V., The Hague Shell Method Series Total Carbon Total Dissolved Solids Total Organic Carbon Total Oxygen Demand Tilted Plate Interceptor Thornton Research Centre
KSLA
MLM OWTC PPI SIPM SMS TC TDS TOC TOD TPI TRC
P U ~ 1-4 C
SlPM Deoilinl: Monvctl, EP 93-1315, Rrv 1.1.Nov 1993. File nctmr = 1INTRO.DOC
2.1.
GENERAL
Each waste water stream is unique, with characteristics defined by a wide range of variables such as the water source, processing operations and directly or indirectly added chemicals. Correct characterisation of the waste water stream is essential to ensure the appropriate selection, design and operation of any deoiling system. This chapter discusses a number of the elements which define the characteristics of a waste water stream.
2.2.
2.2.1.
Produced water
The major source of waste water from production of oil.
The main component of produced water is normally the formation water that is initially present in the reservoir. Formation water should be regarded as being uniquely different from other waters, having existed for millions of years in contact with rock minerals and hydrocarbons, typically under conditions of high temperature and pressure. The produced water may also contain fluids associated with enhanced recovery schemes, particularly injection water. Breakthrough of injection water or other fluids associated with enhanced recovery schemes (e.g. polymers) to the producing wells will result in a change in the character of the produced water. The largest volumes of produced waters are associated with oil production, with gas production having significantly lower rates of produced water. Table 2.1 illustrates the magnitude of the waste water streams produced from a selection of oil and gas platforms in the North Sea. It can be seen that the waste water production from the oil platforms is several orders of magnitude greater than that of the gas platforms.
Table 2.1 Typical hydrocarbon discharges from a selection of North Sea oil and gas production platforms (1989) Oil platforms Gas platforms
Number of platforms measured Total oil or gas production Total produced water Total hydrocarbon discharge (11 Dispersed oil concentration Dissolved oil concentration Polar hydrocarbonconcentration smVd m3/d tonne/y mgn mgn msn
12
15
230.1
481.9
483.9
2.2.2.
Ballast water
Ballast water is a waste water stream generally associated with the storage of oil. The major sources of ballast water are;
SIPM Droilinfi Mwwol. EP 93-1315. Rrv 1.1. Niiv 1993, File ~i<orte = 2CllAP.DOC
P q e 2-1
Ballast waters are relatively cold in comparison with production waters with temperatures typically ranging from 5C to 20C. The hydrocarbon concentration can vary widely, ranging from clean water to slugs of hydrocarbons. Depending on the ballast water intake location and local environmental conditions, ballast water may contain significant quantities of suspended solids such as mud, sand, silt, organic and animal matter.
There are several cases of GBS structures which discharge displaced ballast water with hydrocarbon levels below 40 mg/l without any deoiling treatment. However provision should generally be made for some form of treatment of displaced GBS ballast waters to provide protection against accidental discharges of hydrocarbons. Passive methods such as buffer water ceils could be -used to provide suitable protection.
2.2.3.
Process water
Process water is secondary water generated as a result of the processing activities undertaken during the production of hydrocarbons. Process water can originate from a wide range of sources including;
0
Wash water used for crude oil desalting. Condensed vapours from glycol regeneration equipment. Water condensed during the compression of water saturated gas streams. Water associated with the injection of treatment chemicals.
The importance of the process water streams is dependent upon their magnitude relative to other water streams. In the case of gas platforms which often have low production rates of produced water, the process water can be a significant fraction of the waste water and may dominate the characteristics of the overall waste water stream.
2.2.4.
Drainage water
The drain system associated with E 8, P production sites collects water from a wide variety of sources.
P U ~ C 2-2
SlPM Droiliiq Mo~~trrrl, EP 93-1315, Rev 1.1. Nov 199.7. File mime = 2CIiAP.DOC
Closed drain systems will normally collect produced or process water, typically from the draining of process vessels. Open drain systems will typically collect drainage from surface area drainage and tundishes etc. The majority of the water stream in the open drains system will be intermittent run off from rain or hosing.
Drainage water will typically exhibit the following differences from either production or process water; Flow rates are intermittent, resulting from operations such as vessel draining, rain water, hosing and housekeeping activities. In addition to hydrocarbons and contaminants associated with the production stream, open drains water may contain other contaminants such as lubrication oils and greases from rotating equipment, diesel oil spillage and any other fluids or materials entering the drains by design or accident. Open drains waters will contain dissolved oxygen. Mixing of oxygenated drainage water with other waters may result in scaling or corrosion. Due to the relatively short contact time, hydrocarbons associated with rain water or wash down water are more likely to be dispersed rather than dissolved and thus potentially easier to treat. Information on typical drain system loads due to rainwater, hosing, deluge systems etc. and guidelines for the sizing and design of drainage systems are given in DEP 34.1 4.20.31 -Gen., Drainage and Primary Treatment Facilities.
2.2.5.
Other waters
Other waste water streams which may be discharged from E & P operations include cooling water, sewage effluent, waste cuttings and drilling mud. The treatment of these categories of waste waters is not addressed in this manual.
2.3.
2.3.1.
Poxe 2-3
2.3.1.2.Dissolved hydrocarbons
Some hydrocarbons are partially or completely soluble in the water phase. Table 2.2 lists the solubility of various pure hydrocarbons in fresh water at 15"C, illustrating that the lower molecular weight hydrocarbons and aromatic hydrocarbons have the highest solubility.
Table 2.2 Solubility of hydrocarbons in water (mgll at 15C) ALKANES AROMATICS
cycio
1 Ring
___-_--
Notes: 1. These solubilities are lor binary systems of a single hydrocarbonand fresh water and are only indicative for produced waters. Solubility levels in produced waters may be different due to lactors such as: a) The effect of the temperature and pressure in the reservoir where the water is in contact with the hydrocarbons. b) The presence of other species dissolved in the water phase such as inorganic salts and soluble organic species such as organic acids. c) Preferential partitioning of the hydrocarbons to the hydrocarbon phase when both hydrocarbonand water phases are present. 2. Source: Superseded SlPM Dehydration/Deoilingmanual, EP 89-0150
Crude oil streams are typically composed of higher molecular weight aliphatic and aromatic hydrocarbons which have a low solubility in water. Thus the dissolved oil content in the waste water from oil production operations is normally relatively low. This usually allows the waste water streams from crude oil operations to be treated to typical discharge standards by removal of the dispersed hydrocarbons alone. For gas production operations the dissolved oil content may be more significant. Gas hydrocarbon streams are composed of low molecular weight hydrocarbons and may also contain significant quantities of relatively soluble low molecular weight aromatic hydrocarbons such as benzene, toluene and xylene. The higher solubility of hydrocarbons associated with gas production is illustrated in Table 2.1. It can be seen that the typical level of dissolved hydrocarbons from the gas platforms is 482 mg/l, compared to only 6 mg/l for the oil platforms. For some gas processing installations, a significant quantity of the aromatic hydrocarbons in the waste
PUXC 2-4
SlPM Deoilinji Miiniml, EP 93.1315, Rev 1.1. Nov 1993. File nctme = 2CHAP.DOC
In addition, most hydrocarbon analysis procedures require the extraction of the hydrocarbons from the water phase using a solvent. Polar hydrocarbons are not efficiently extracted by some solvents and are thus not included in the subsequent hydrocarbon analysis. However, some analysis methods (e.g. Total Organic Carbon) will measure polar compounds and will often indicate a hydrocarbon concentration far higher than that measured through conventional analysis methods. As for dissolved hydrocarbons, the majority of deoiling equipment currently installed in E & P operations is not capable of reducing the polar hydrocarbon content of waste water.
2.3.2.
Treatment chemicals
A wide variety of treatment chemicals may be present in waste water streams. Typical examples include corrosion inhibitor, scale inhibitor, demulsifiers, hydrate inhibitors, biocides, flotation aids etc. Other incidental chemicals may also be present such as detergents used for wash down purposes. The effect of such chemicals can be significant in the selection and design of deoiling equipment as; Many treatment chemicals are surface active and may stabilise small hydrocarbon droplets in the water phase. The corrosion inhibitors used in gas production operations and the demulsifiers used to assist oil dehydration can sometimes result in such stabilisation. The small droplets may be very difficult to separate with conventional deoiling equipment. Some treatment chemicals may be incompatible with other chemicals. Examples are demulsifier chemicals interfering with subsequent deoiling chemicals, or deoiling chemicals reacting with dilute polymers present in the water as a result of enhanced recovery schemes. Efforts should be made to reduce the use of treatment chemicals whenever possible on the basis of minimising both operating costs and the ingress of additional chemicals into the environment.
2.3.3.
Suspended solids
Suspended solids in waste water can originate from a number of sources such as formation solids, corrosion and erosion products, precipitates and as by-products of biological processes within the process facilities. Solids may also originate from process equipment such as the degradation of molecular sieve or packing materials. The treatment and discharge of drilling cuttings and drilling mud is
Niiv
Puge 2-5
Solids may trap or collect other contaminants. For example, solid particles may be oleophilic, attracting and trapping hydrocarbons which will be discharged with the solids. Discharged solids may accumulate as mud or silt in the local environment.
Discharged solids may result in turbidity in receiving environments with poor dispersion characteristics. Such turbidity may have an environmental impact as well as being undesirable visual pollution.
Suspended solids may have a significant impact on the design of deoiling equipment. Erosion and the effects of solids accumulation in deoiling equipment must be considered. In some cases equipment will be specifically designed to allow the accumulation of solids which can be periodically removed. The "Sand Wash Design Manual" EP 93-1270, due to be issued in the 4th quarter of 1993, contains additional information on topics including: The transportation, deposition and accumulation of solids in production systems. The design of equipment and jetting systems for the collection and removal of solids. The handling and disposal of solids contaminated with hydrocarbons.
2.3.4.
Heavy metals
The presence of heavy metals in waste waters can be of concern due to their potential toxicity and propensity for bio-accumulation. However not all heavy metals are regarded as dangerous. Table 2.3 gives a guide to the relative toxicity of a range of heavy metals and inorganic compounds.
Table 2.3 Relative toxicity of heavy metals and inorganic compounds Heavy metal or Environmental Heavy metal or inorganic Ranking inorganic compound compound Aluminium 1 Manganese Mercury Barium 1 Molybdenum Boron 1 Nickel Cadmium 3 Calcium Phosphorus 1 Potassium Chromium 3 Cobalt Silicon 1 Copper Sodium 3 Iron Strontium 1 Lead Sulphate 3 Lithium Vanadium 1 Magnesium Zinc 1 Rankings: 1 ... 1 critical 2 ... Toxic, but rare or having low solubility 3 ... Highly toxic and relatively accessibleEnvironmental Ranking
1 3
2
3 1 1 1 1 1 1
2
3
Source: Shell Expro's Wastes, 1989, Safety and environmental affairs department, ref
2.3.5.
Salinity
The salinity of water is typically expressed as the concentration of Total Dissolved Solids (TDS), indicating the quantity of dissolved inorganic salts present in the water. The salinity of the waste water should be considered for the following reasons;
For surface disposal, the salinity of the discharge water should not be significantly different from the salinity of the receiving environment. This should encompass both the discharge of saline water into fresh waters and the discharge of fresh water into saline waters (e.g. inshore).
_ _ ~
~
P(ixC
2-6
SlPM Deoilinx
M(iiiud,
2.3.6.
pH
The pH determination of water is a relatively reliable indication of its acidic or alkaline tendency. However it is not a measure of the actual acidity or alkalinity in a water sample. ASTM D 1293-78 discusses the measurement of pH while ASTM D 1067 discusses the measurement of actual acidity or alkalinity. The pH of the waste water is subject to regulation in some countries which typically require the pH of discharged waste waters to be between 5.5 and 9.0 Alkaline waste waters with a pH in the range of 8-10 may react with components of the hydrocarbon stream to form surfactant type chemicals. These surfactants may assist in stabilising emulsions.
2.3.7.
Hardness
Hardness in water is generally caused by the presence of calcium and magnesium ions, though any polyvalent cation can contribute to hardness. Hardness in water can result in scale formation in process equipment. The release of dissolved CO, during depressurisation may also alter the hardness characteristics of water.
2.3.8.
Thermal contamination
Although not strictly a contaminant, the temperature of discharged waste waters may have an impact on the environment. The impact will be dependent on factors such as the temperature differential to the receiving environment and the physical extent of the temperature gradient. The temperature will also affect the density and viscosity of the waste water. These variations must be accounted for in the design of waste water treatment equipment and when modelling the dispersion characteristics of waste water discharges. The temperature of waste water discharges may be subject to regulation, especially in the case of discharges into inland water bodies such as rivers and lakes.
2.3.9.
Dissolved oxygen
From an engineering standpoint, the presence of oxygen in a water stream is very important due to its potential role in the corrosion of process piping and equipment and in the resultant corrosion products in effluent waters. Produced waters do not normally contain any dissolved oxygen, however oxygen may be introduced into the process through open equipment and tanks or through the use of aerated waters such as fresh water used for desalting. From an environmental viewpoint, the levels of oxygen in discharged water can have a significant impact on the receiving environment. Discharge of oxygen free water into surface waters may result in an oxygen deficiency in the local aquatic environment. Some countries have regulations governing the quantity of dissolved oxygen that must be available in waste water discharges. Conversely, the presence of contaminants in the waste water can affect the level of dissolved oxygen in the receiving environment by consuming oxygen through biological and/or chemical oxidation of the contaminants. The oxygen demand of a waste water stream is an indication of the oxygen depletion that may be imposed on the receiving environment. Oxygen demand is measured and expressed in several different ways.
2.3.9.1.
i~iiiiie =
ZCI/AP.OOC
Pujie 2-7
2.3.9.2.
2.3.9.3.
2.4.
Pup2 2-8
SlPM Deoilinl: Mcrnuctl. EP 93-1315, Rev 1.1, Nov 1993. File n(ime = 2CHAP.DOC
10
9
8
0.1
10
Particle size (urn)
100
1000
100
90 80
70
60
50
40
30
20
10
0
0.1
1
10
Particle size (urn)
100
1000
ii(inic =
ZC/fAAp.DOC
P q e 2-9
Pop2 2- IO
SlPM Deoilinx
Moiiiid.
3.Emulsions
3.1. 3.1.1.
DEFINITIONS General
An emulsion can be simply defined as a dispersion of one immiscible liquid in another. By this definition, any mixture of two liquid phases is an emulsion, regardless of whether the dispersion of the phases is stable or unstable. In practice, emulsions generally have some degree of stability that prevents them immediately separating into non-dispersed phases. However stability can range from extremely stable emulsions requiring special treatment to break, to relatively unstable emulsions which will separate in a finite time under suitable conditions. Thus the term emulsion applies to most dispersions of hydrocarbons in water encountered in E & P operations, from tight, stabilised emulsions to relatively unstable mixtures. Due to the relatively low volume of hydrocarbons compared to the volume of water, the oil-in-water emulsions encountered in deoiling processes have relatively simple behaviour. The bulk of the emulsion is formed by the continuous water phase and thus physical parameters such as viscosity are relatively well defined. Emulsion characteristics for the water-in-oil emulsions encountered in oil processing may be significantly more complex involving problems such as significant quantities of evolved gas, high viscosity and phase inversions. For a more detailed discussion of water-in-oil emulsions the user is referred to the emulsion references listed in the bibliography of this manual and the SlPM Dehydration/Deoiling manual.
3.1 2.
Distribution of phases
Emulsions are characterised by a distribution of two liquid phases. The phase present in the form of discrete droplets is known as the dispersed or internal phase, while the phase which forms the matrix in which the droplets are suspended is known as the continuous or external phase. The two emulsions typically encountered in oil and gas production operations are; Hydrocarbons droplets dispersed in a continuous water phase, referred to as an oil-in-water, o/w or reverse emulsion. Water droplets dispersed in a continuous hydrocarbon phase, referred to as a water-in-oil, w/o or normal emulsion. More complex emulsions can occur, sljch as an oil-in-water emulsion forming droplets within an oil phase, forming an oil-in-water-in-oil emulsion. However such complex emulsions are considered to be rare. The deoiling processes covered in this manual are designed for the first type of emulsion, hydrocarbon droplets dispersed in a continuous water phase.
3.1.3.
Stability
Depending on how readily the phases can be separated, emulsions can be classed as unstable or stable. As will be discussed later, simple emulsions are by nature unstable and in the absence of external factors an emulsion will generally disengage into separate phases. However, in practice most emulsions are not simple and are often stabilised by the presence of some form of emulsion stabiliser. The emulsion stabiliser prevents dispersed droplets from coalescing or slows the coalescence to an rate that may be unacceptable for processing activities.
3.1.4.
Size distributions
Emulsions can be broadly characterised by the size of the droplets of the dispersed phase. Primary emulsions have a droplet diameter typically larger than 100 pm. Due to the large droplet size such emulsions are usually relatively easy to separate. Secondary emulsions have a droplet diameter typically between 0.5 pm and 50 pm. This encompasses many oil-in-water emulsions encountered in E & P waste water treatment operations.
3. Emulsions
Micro emulsions have droplet sizes in the order of 0.01 pm to 0.1 pm and are optically transparent.
3.2. 3.2.1.
3.2.2.
3.3. 3.3.1.
As a contrast, the majority of hydrocarbons associated with oil and gas production are non-polar. As such there is little attraction between the water molecules and the hydrocarbon molecules and the two liquids are regarded as insoluble or immiscible.
In practice, there will usually be some limited solubility between even immiscible phases. Solubility of hydrocarbons in water is discussed in more detail in Chapter 9.2.
3.3.2.
Surface tension
Molecules within a liquid or gas are subject to short range attractive (van der Waal) forces. In the bulk of the liquid, each molecule is surrounded on all sides by other molecules, thus the attractive forces are relatively evenly distributed.
P U ~ 3-2 C
SIPM Dooiling Mitnuiil, EP 93-1315. Rev 1.1, Nov 1993. File nume = 3CHAP.DOC
3. Emulsions
However, the molecules at the interface between a liquid and a gas, not being completely surrounded by other liquid molecules, are subject to an unbalanced attraction which has the net result of an attractive force directed inward, normal to the surface. This effect is illustrated in Figure 3.1. The smaller the surface, the lower the free energy associated with the surface, thus the surface of the liquid has a tendency to contract. This effect is apparent as surface tension. Surface tension can be defined and measured as the work required to generate an additional unit of surface area.
~
Air
HIXtZWIP
3.3.3.
Interfacial tension
When two immiscible liquids are placed in contact, an interface between the two phases will result as shown in Figure 3.2. Unlike a gashquid interface, there will be some attraction between the molecules of the two liquids due to the relatively close proximity of molecules at the interface. However, the attraction will be stronger to the molecules of the same type in the bulk of the liquid, leading to an imbalance of forces and the creation of an interfacial tension. This effect will be present in both phases. Hence it is to be expected that the value of the interfacial tension will lie between the individual surface tensions of the two phases. Any system will attempt to move towards a state of lower energy. The forces present at the interface between the two phases represent a form of energy and the system will move to minimise this energy by the following means. As a sphere has the lowest surface area per unit volume, in the absence of other forces a droplet of the dispersed phase will adopt a spherical shape.
2:
For a given volume of liquid, one large droplet will have less total interfacial area than two smaller droplets. As the interfacial area is associated with energy (interfacial tension), smaller droplets will tend to coalesce into larger droplets to minimise the energy associated with the interfacial tension.
Thus, the presence of interfacial tension will cause the dispersed droplets in an emulsion to naturally coalesce. The greater the interfacial tension, the greater the tendency for the droplets to coalesce. However, in practice other influences are commonly present that will act to stabilise the emulsion and inhibit coalescence.
3.3.4.
Eq. 3.1
Where:
interfacial tension (mN/m or dyne/cm) water/oil interface solid/oil interface solid/water interface
Puxe 3-3
SlPM Duoilinx Mioiirrrl. EP 93-131s. Rev 1.1, Nov 1993. File IIirnw = 3CfIAP.DOC
3. Emulsions
The solid is completely water wetted if 0 = 0 and only partially wetted otherwise. In practice, contact angles of 0 < 90" are often considered to represent "water wetting" and values of 0 > 90" to represent "non water wetting". This assignment is rather arbitrary as it is based on correlation with the visual appearance of droplets on surfaces. Wetting considerations can play an role in the stabilising of emulsions. Solids may give additional mechanical strength to an interface, supporting an emulsified state. The most stable emulsions will occur when 0 = 90" as the solids will be supported in the interface by both phases. Combining Young's equation with oriented wedge theory (ref 1.08.1 .a) predicts that fine solids which are water wetted will be better at stabilising an oil-in-water emulsion while solids which are oil wetted will be better at stabilising a water-in-oil emulsion.
3.3.5.
Emulsion stabilisers
Factors affecting emulsion stability By definition, the stability of an emulsion is a time dependant characteristic. An emulsion that takes several days to disengage into separate phases is unstable as coalescence is slowly occurring, however for practical processing purposes, such an emulsion is considered stable. An emulsion may be stabilised by one or more of the following factors.
3.3.5.1.
Low interfacial tension. A low interfacial tension means there is less driving force to minimise interfacial area by coalescence and it is energetically easier to maintain a dispersed state. Many emulsion stabilising agents such as surfactants act by lowering the interfacial tension.
Mechanically strong interface film. A strong interfacial film acts as a barrier to coalescence. The mechanical strength of a film may be enhanced by the absorption of solids or close packed surfactant molecules.
0
Electric double layer repulsion. The repulsion between similarly charged droplets acts to prevent droplet collision, agglomeration and coalescence. Small volume of dispersed phase. Reduces the probability of collisions between dispersed droplets.
______
: I : -
-z -_ _z -r -_ -_ _ _ -_ -_ -_ _-Figure 3.3 illustrates how a surfactant behaves in an oil~ i_ i _-___ _- _ _ __ _ _ _ ---- -______-_ ___ --_ _-__ in-water emulsion. The oleophilic end of the molecule ----------------HlXRMP aligns itself towards the hydrocarbon phase while the Figure 3.3 hydrophilic end is orientated towards the water phase, Surfactant stabilising an forming a protective "skin" around the droplet. The oil-in-water emulsion surrounding water phase only "sees" the hydrophilic end of the surfactant, while the hydrocarbon droplet only "sees" the oleophilic end. This reduces the interfacial tension between the two phases, hindering the coalescence process and stabilising the emulsion. The presence of the surfactant molecule at the interface may also increase the interfacial viscosity, providing a mechanical resistance to droplet coalescence.
_---__
Surfactants are classified as either anionic, cationic or non-ionic according to the nature of the hydrophilic end of the molecule. Examples of these surfactants are given in Table 3.1 and discussed below. Anionic surfactants are typically oils and alcohols, organic amine-fatty acid soaps and sulphated aliphatic and aromatic compounds where the hydrophilic section is negatively charged. The best
Puge 3-4
SIPM Droilinl: Monuctl, EP 93-1315, Rev 1.1. Nov 1993, File nome = 3CHAP.DOC
3. Emulsions
known example are common soaps. Cationic surfactants are characterised by the hydrophilic section being positively charged, such as quaternary ammonium salts. Non-ionic surfactants are organic molecules which do not ionise in solution. The majority of demulsifying chemicals used in the oil industry to assist the destabilisation of water-in-oil emulsion are of the non-ionic type such as esters containing water soluble groups which are polymers of either ethylene and/or polypropylene oxide.
Table 3.1 Classification of surfactants Class Anionic Na stearate Examples
Na dodecyl sulphate
Na dodecyl benzene sulfonate Cationic Laurylamine hydrochloride Cetyl trimethylammonium bromide Non-ionic
Source:
Em( ions. Fundamentals and applications in the petroleum industw, edited by Schamm, L.L., Ref.1.OB.1 .a
Oil-in-water emulsions may also be stabilised by a high pH (8-10) in the water phase. The alkaline components of the water may react with organic components to form soap like molecules. These molecules may then act as surfactants and stabilise emulsions. Some treatment chemicals may also act as emulsion stabilisers. Corrosion inhibitors are often designed to be highly surface active and as a consequence may be very effective emulsifiers. Overdosing of demulsifiers (treatment chemicals designed to destabilise and promote the coalescence of a water-in-oil emulsion) may result in stabilisation of an oil-in-water emulsion in the separated water phase.
3.3.5.3.
Electrical charge The droplets of the dispersed phase may carry an electric charge. This charge could be a surface characteristic of the dispersed phase, but is most often associated with the presence of ionic surfactants at the droplet interface. Ionic surfactants arrange themselves with the charged hydrophilic end of the surfactant molecule facing into the continuous water phase. This gives the external surface of the hydrocarbon droplet an external charge, the polarity of the charge being dependent upon the ionic characteristics of the surfactant. In most cases, the external surface of an oil-in-water emulsion tends to be negatively charged. However, the presence of an external charge layer on the hydrocarbon droplet causes a further realignment of the ions within the water phase. Positive ions will be attracted to the negative surface charge, forming a diffuse positively charged region around the droplet. This is referred to as the double layer effect. The net result in an emulsion is that the dispersed droplets will often carry an electrical charge and will repel each other, reducing the probability of droplets colliding and coalescing. The double layer effect is usually more effective at stabilising oil-in-water emulsions than water-in-oil emulsions. The continuous water phase in an oil-in-water emulsion has many small, mobile ions in solution which readily accumulate to form an effective double layer around the dispersed hydrocarbon droplets. Continuous hydrocarbon phases do not contain the same small mobile ions and are thus less effective at such charge based stabilisation.
3.3.5.4. Solids
The presence of fine solids may have an influence on the stability of an emulsion by accumulating at the interface between the phases. Such solids may include;
SIPM Droilinl: MIIIIIIIII, EP 93-13l.~.Rev 1.1. NIIV 1993. File mime = 3CIiAP.DOC
P q e 3-5
3. Emulsions
Formation solids Insoluble asphaltenes and resins Precipitated scales e.g. calcium carbonate, calcium sulphate, barium sulphate. Corrosion products e.g. iron oxides, iron sulphides Wax crystals To have a significant influence the solids should be small compared with the dispersed droplet size, allowing the solid particles to be absorbed into the interface between the liquid phases. The influence of solids on coalescence is dependant on a variety of factors such as the surface characteristics of the solids and which phase they are preferentially wetted by. In general, particles which are wetted by the water phase will tend to stabilise an oil-in-water emulsion, while conversely, solids which are preferentially wetted by the hydrocarbon phase will tend to stabilise water-in-oil emulsions. The wettability of solids is discussed in section 3.3.4. However the mechanisms by which solids affect emulsions are complex and exceptions to these general rules can often occur. Solids may influence emulsion stability through other paths such as forming bridges between droplets or influencing the surface charge characteristics of the dispersed droplets.
3.3.5.5.
3.4.
3.4.1.
3.4.2.
It should be recognised that the behaviour of demulsifiers and deoilers may not be complimentary. For
P U ~ 3-6 C
SIPM Deoilinx Morrt~crl. EP 93-1315. Rrv 1.1, Nvv 1993, File nome = 3CHAP.DOC
3. Emulsions
example, a demulsifiers added to crude oil to assist in its dehydration may result in the formation of a stable oil-in-water emulsion in the separated water, especially if the demulsifier is overdosed. 3.4.2.1. Composition of deoilers Because the emulsion stabilising agents will be different for each application, each deoiler has to be tailored to obtain the optimum results. A typical deoiler consists of a number of chemicals designed to reverse the effect of each emulsion stabiliser: Surfactant stabilisation can be overcome by reversing or hindering the oleophilic/hydrophilic nature of the surfactant. Stabilisation by solids can be overcome by altering the surface characteristics of the solids, allowing the solids to disperse from the interface into one of the phases. Electrical charge stabilisation can be overcome by allowing the charge to be redistributed or hidden. For oil-in-water emulsions the emulsion stabilising surfactants tend to be anionic in nature. Thus many deoiler chemicals typically contain mixtures of cationic surface agents and polymers. The cationic agents neutralise the anionic characteristics of the emulsifier, overcoming the electrical repulsion of the hydrocarbon droplets. Deoilers are typically supplied as 25-50% solutions of the active chemicals dissolved in a water soluble solvent. 3.4.2.2. Testing and selection of deoilers Testing of deoiling chemicals in laboratory or bottle type tests presents a number of problems such as the relatively low hydrocarbon concentrations, the time dependant nature of the emulsion size distribution and emulsion stability and the difficulty in obtaining and preserving representative samples of a dilute emulsion. Because of these problems, laboratory or bottle type tests should only be used for the screening of a range of deoilers. The final performance and optimum dosage rate for a deoiler should then be confirmed through field trials with the deoiling equipment. In addition to the performance of the deoiler in destabilising the oil-in-water emulsion, the selection of the deoiler should also consider the following; Temperature. The deoiler should work satisfactorily over the full range of process temperatures that may be encountered in the effluent treatment equipment. Although higher temperatures are generally favourable for destabilisation of emulsions, the deoiler should remain stable and effective at these temperatures. Similarly, the deoiler should also operate efficiently when the temperature is at a minimum such as in winter. Treatment chemicals. The interaction of the deoiler with other chemicals should be considered. Some treatment chemicals may hinder the performance of the deoiler, leading to excessive deoiler consumption. If demulsifiers are used in the upstream processing for destabilisation of water-in-oil emulsions, the demulsifier and deoiler should be compatible. Environmental impact. Being injected into the effluent stream, a proportion of the deoiling chemicals will be discharged into the environment with the treated water. As such the deoiler and its carrier fluid should be suitable for release into the environment. The performance of a deoiler may not be constant with time. Changes in the characteristics of the production well stream or the upstream processing operations may require the selection or dosage rate of the deoiler to be investigated. Similarly, if significant increases in deoiler consumption are required to maintain satisfactorily performance, the selection and dosage rate of the deoiler should be reviewed. 3.4.2.3. Deoiler injection location and dosage rates Deoiler chemicals should typically be injected as soon as possible afler the bulk oil and water separation stage as the presence of the deoiler in the water stream should help to minimise subsequent emulsification and allows the maximum time for coalescence. For example, injection upstream of a water level control valve would ensure good mixing of the deoiler and water stream and help to prevent the
SlPM Droilinji Miinucil. EP 93-1315, Rev 1.1, Nov 199.7, File niinie = 3CliAP.DOC
Puxe 3-7
3. Emulsions
formation of a stable emulsion. Deoiler injection rates should be controlled to ensure correct dosage. This may preclude injecting at location where the water flow is intermittent. Dosage rates are typically of the order of 5 mg/l. The efficiency of a deoiler may be reduced though overdosing and in some cases may even result in stabilisation of the emulsion. The dosage rate should be optimised on the basis of field trials.
3.4.3.
3.4.3.2. Acidification
As noted in section 3.3.5.2, a high pH in the water phase can stabilise the emulsion by reaction of the alkaline components in the water with the hydrocarbons. The addition of acids to the system may counter this effect and result in better deoiling performance.
Changes to the water pH may also influence the surface charge of the dispersed droplets. Reducing electrical charge would reduce the repulsive forces between the dispersed droplets and thus assist coalescence.
Pujic 3-8
SlPM Droilinl: Mn~~irol. EP 93-1315. Rrv 1.1. Nirv 1993. Filr ntrrne = 3CHAP.DOC
4. Water disposal
4.1.
GENERAL
The water produced as a result of production operations needs to be disposed in a responsible and environmentally acceptable manner. There are three major forms of water disposal. Surface disposal Water injection Disposal injection Surface disposal is generally subject to regulation and is a potential source of environmental pollution. Regulatory restrictions, as well as a Group commitment to minimising discharges into the environment, will see subsurface disposal techniques become more important in future operations. The different types of water disposal methods often set the performance criteria required from deoiling equipment, such as the regulatory limits on hydrocarbon levels for surface water disposal or reservoir imposed limitations on solids and hydrocarbon content imposed for subsurface disposal.
4.2.
4.2.1.
Because of the potential impact on the environment, the discharge of effluent waters is normally governed by regulatory limits set by national or regional authorities. Table 4.1 indicates the allowable hydrocarbon discharge concentrations for coastal and inland discharges while Table 4.2 lists the allowable levels for offshore discharges.
Table 4.1 National coastal and inland oil-in-water limits
____42 20
----_
_--_Average oil content (mg/l)
_____
20 29
Country Belgium Denmark France Italy Malaysia Nigeria Norway Portugal Switzerland Germany
5 5 20
1 0 1 0 5-20 5-20
lo
1 0
5
_____
II~IIII= C
4CiiAl.DOC
Puxe 4-1
4. Water disposal
Table 4.2 National offshore oil-in-water limits
OFFSHORE
Country Abu Dhabi Australia (Victoria) Canada Denmark France India Malaysia Netherlands Nigeria Nowav PARCOM Spain United Kingdom USA Maximum oil content (mgn)
__---
15 50 50
20 40
EWPt
15
_-_-_
29
* 4% of samples taken
The discharge limits for territorial seas and offshore continental shelf installations in the USA were lowered in January 1993. The new limits are an average of 29 mg/l per month with a maximum of 42 mg/l per day. Both new and existing installations will be required to satisfy the more stringent regulations. In general the regulations covering water discharges are most stringent for inland locations, with the regulations often controlling a wide variety of substances including both dispersed and dissolved hydrocarbons, heavy metals, biological oxygen demand etc. In contrast, regulations covering offshore effluent discharges are less coherent. Limits have typically been set on the basis of expected performance levels of available deoiling equipment and not on environmental impact considerations.
It should be noted that regulations from different countries or within the same country often have considerable variation in areas such as defining which components are considered hydrocarbons, whether dissolved and polar hydrocarbons are included and which hydrocarbon analysis method should be used.
A good example is the gravimetric analysis method required by some regulations tends to measure a lower hydrocarbon content than the infrared analysis method required by other regulations. Some regulations allow gas sparging of the sample which strips volatile hydrocarbons from the sample. Due to these variations, a limit set or measured under one set of regulations is not always directly comparable to a limit under a different set of regulations.
Table 4.3 gives a qualitative guide to the surface appearance of water containing small quantities of hydrocarbons. Although each hydrocarbon and water combination will be different, for this particular oil/water combination it is apparent that it is difficult to visually detect low levels of hydrocarbons.
Effect on surface of water sample Not visible Silvery sheen Traces of colour Bright colour Dull colour Dark colour
I
Source:
P U ~4-2 C
SlPM Deoilinx M~rrtu~il, EP 93-1315, Rev 1.1, Nov 1993, File nume = 4CHAP.DOC
4. Water disposal
4.2.2. Setting of environmental discharge standards
In addition to regulatory limitations, the treatment of waste water streams should be governed by local environmental considerations. An Environmental Quality Objectives (EQO) approach can be followed to establish suitable effluent quality targets. The EQO method consists of the following steps; Evaluation of the local environmental characteristics. Identification of all potential contaminating components of all effluent streams. Identification of environmental characteristics sensitive to effluent discharge levels. Consideration of the potential end use of waters in the receiving environment e.g. drinking water supply, agricultural use.
0
Determining the distribution, fate and impact of all substances contained in the effluent steam. Impact should consider factors including toxicity, persistency, accumulation and biodegradability.
Taking all these factors into consideration allows the setting of realistic and environmentally responsible standards governing the level of contaminants in waste water discharges to ensure minimal environmental impact. In some instances, the EQO approach may lead to the adoption of standards that are more stringent than that required by local regulations. However, in other cases the EQO approach may be used as a logical and defensible basis to support the setting of realistic discharge levels for a particular environment. SlPM EP0/6 should be contacted for more information on the EQO approach.
4.3. 4.3.1.
4.3.2.
Water compatibility
Water injection of produced water is only possible if the water is determined to be compatible with the production reservoir. The investigation of water compatibility should address the following considerations:
0
Compatibility with the formation. Chemical incompatibility may result in the expansion of clay minerals or oxidation reactions due to the presence of oxygen (most injection water is maintained oxygen free). Physical incompatibility may result in the migration of fine solid particles through the formation (either carried by the injection water or dislodged from the formation) with the potential for blocking pores and consequent reduction in formation permeability. Compatibility with formation fluids. Incompatibility with formation fluids can result in changes in the chemical equilibrium of the formation fluids, potentially leading to scale formation in the
Noit
1993, Filr
twiie
= .IC//AP.DOC
Puge 4-3
4. Water disposal
reservoir, tubing or in surface production facilities.
Compatibility with other injection waters. In some cases, waste water will form only part of the total volume of required injection water. In this instance the compatibility of the waste water with the other injection waters (e.g. sea water) must be established, as well as the compatibility of the combined waters with the formation itself and the formation fluids.
4.3.3.
Permeability impairment
Treatment of water before injection is required to avoid potential impairment of the permeability of the formation. Table 4.4 lists potential means of permeability impairment and references the sections of the current SlPM Water Injection Manual (EP-63600) where additional information can be found. Of these potential means of permeability impairment, the removal of suspended solids and dispersed hydrocarbons from the produced water are of most importance to the selection of water treatment equipment.
Table 4.4 Potential sources of permeability impairment Impairment source Suspended solids Coalescing oil droplets Formationof insoluble scales Pre-engineering evaluation method Method of prevention
Ref
. . . . .
31,
Source water survey Evaluation of filtration specification Source water analysis Analysis of source water and formation water Computer aided scale prediction Dynamic tests of chemical inhibitors Core sample flooding tests Petro-graphicalanalysis Core sample flooding tests Petro-graphicalanalysis Source water analysis Source water analysis
EP-63600, August 1985
.
0
Fine filtration Fine filtration Fine filtration Emulsification Prevent commingling of incompatible fluids or use chemical inhibitors Sulphate removal membranes Modify water injection program Chemical injection Modify water injection program Chemical injection Inject chemical biocides Materials and coatings selection Chemical inhibitor injection Cathodic protection
L
3 . 2 . 1 3.2.1 3.2.3 3.3.3 3.2.2 4.4 4.3 4.3 3.2.5 7.2
6.0
. . .
I
4.3.3.1.
Solids removal
Solids present in injected water have the potential to be trapped in the formation around the well bore, resulting in a flow restriction and a deterioration in injectivity. Such blockage will adversely affect the ability of the injection well to accept the requisite waste water volumes. Individual reservoirs differ in tolerance for both the quantity and the size distribution of the solids in the injection water. Factors that will affect the ability of the reservoir to tolerate solids include; The permeability and pore structure of the basic reservoir material. The degree of fracturing present in the reservoir. The physical properties of the hydrocarbons present in the reservoir. Core flooding tests can give some indication to the tolerance of the reservoir to the presence of solids. However field experience often contradicts the results of core flooding tests, either by injectivity impairment of tolerant reservoirs or in the unexpected tolerance of supposedly tight reservoirs. Typical quality requirements for water injection of sea water in the North Sea are 98% removal of solid particles larger than 2 pm with a particle number count of less than 25 parlicl,es per 0.05 ml of water. This corresponds to the typical water quality that can be achieved with conventional filtration equipment. A well-head guard filter can be used to achieve a further reduction in solids by the removal of up to 100% of particles larger than 0.6 pm.
Pujic 4-4
SIPM Deoiling Mitiiurrl. EP 93-1315, Rev 1.1, Nov 1993, File nitme = 4CHAP.DOC
4. Water disposal
However, the setting of excessively strict water injection specifications is very expensive in terms of additional process equipment, particularly for offshore installations. Specifications should not be set as simply the best achievable quality, but should be justified by consideration of all relevant information. Issues such as down hole contamination of the water with corrosion/erosion products, the thermal fracturing of reservoirs and the costhenefit analysis of different treatment options should be considered.
4.3.3.2.
Hydrocarbon removal The presence of dispersed hydrocarbons in the injected water can also lead to permeability impairment. Dispersion of the hydrocarbon into the reservoir may result in the formation of a stable emulsion or sludge, often stabilised by the presence of solids. This emulsion may exhibit a very high viscosity and non-Newtonian rheological behaviour, resulting in plugging of the reservoir. In addition, dispersed oil may alter the wetting properties of the formation and may form an oil bank in the proximity of the well bore, also reducing permeability. For many water injection schemes the dispersed hydrocarbons are removed along with the suspended solids by filtration. In this case the hydrocarbon droplet size in the feed stream and the level of dissolved hydrocarbons present will determine the level of hydrocarbons remaining in the filtered water. Typical design levels are less than 5 mg/l of dispersed hydrocarbons.
4.3.4.
The possibility of scale formation from mixing incompatible waters The introduction of bacteria and/or oxygen into the injection water. The optimum rate of water injection for production purposes may not correspond with the rate required for disposal of secondary waste waters. During initial years of production there may be no requirement for any water injection. Flow rates of secondary water may be seasonally variable.
In most instances, waters for injection and secondary sources of water are riot mixed. In these circumstances, even though the bulk of the waste water may be disposed of through water injection, waste water treatment facilities must still be provided for the disposal of secondary waste water streams.
4.4. 4.4.1.
DISPOSAL INJECTION
General
Disposal injection differs from water injection in that the water stream is injected only for the purpose of disposal, not as a means of assisting production rates. Disposal injection injects waste water into subsurface formations other than the production reservoir, such as aquifers or exhausted production reservoirs.
As with water injection, the information provided in this Deoiling Manual is a summary only, concentrating on the aspects of disposal injection relevant to the selection and design of deoiling equipment. For more detailed information the user is referred to the SlPM Water Injection Manual (currently EP-63600, revised edition expected by 1st quarter of 1994).
4.4.2.
iiitine
= 4ClIAP DOC
PuRe 4-5
4. Water disposal
However, there is typically more latitude allowed in the treatment of disposal water than allowed for injection water and there are numerous cases of the disposal injection of waste water with minimal treatment. A more relaxed water quality specification for disposal water is often acceptable on the basis of: The disposal formation may be specifically chosen on the basis of a high tolerance for poor quality disposal water. Stimulation of the disposal formation may be possible. In many cases, water for disposal injection may only need to be treated to level similar to typical offshore surface disposal specifications, i.e. below 40 mg/l dispersed hydrocarbons. This can be used as a starting point for design. However, considering the potential impact on equipment design, these limits should be confirmed through normal reservoir plugging evaluations as discussed in the SlPM Water Injection Manual.
4.4.2.2.
Environmental constraints Disposal injection of waste water should avoid subsurface structures that may be used or linked to sources of water for industrial, agricultural or domestic purposes.
4.4.2.3.
Regulatory constraints Countries which utilise aquifers as a source of water for industrial, agricultural or domestic purposes will often have regulations governing the disposal of waste waters in subsurface structures.
4.5.
4.5.1.
4.5.2.
4.5.2.1.
Disposal options
Export with hydrocarbons Secondary waste streams may often be spiked into the product hydrocarbon stream and exported. This is often possible as the secondary waste stream may be relatively concentrated and small in volume compared to the overall product stream. This is a common method of "disposing" the hydrocarbons recovered from deoiling processes. However, it should be recognised that this method of disposal is simply transferring potential contaminants to downstream processing activities where the same contaminants may need to be removed a second time. In some cases it may be more economic to treat the waste upstream rather than transfer the problem downstream.
4.5.2.2.
Recycling to process Many process schemes recycle secondary waste streams to the start of the process. This is satisfactory provided at some point in the process there is a satisfactory purge of the contaminant from the process systern. Care must be taken to avoid the potential accumulation of contaminants in the process through recycling. For example, the recycling of sludge, such as from oil/water interfaces, should be avoided. Such sludges are relatively stable and are unlikely to break down without additional treatment. As a result they will tend to accumulate in the process. Solids may also accumulate in the process and may eventually reach a stage where they are responsible for the stabilisation of sludges or emulsions.
PUKE 4-6
SlPM Deoilinx Mmiud, EP 93-1315. Rrv 1.1. Nov 1993, File name = ICHAPDOC
4. Water disposal
4.5.2.3. Disposal to atmosphere Some deoiling processes will result in the generation of a waste gas stream, for example stripping of hydrocarbons from water using a gas. The resulting gas stream containing the stripped hydrocarbons is typically discharged to the flare system or fuel gas system, and may be subject to regulations governing discharges to atmosphere. 4.5.2.4.
4.5.3.
4.5.3.1.
Sludges
General Sludges are secondary waste streams containing accumulated solids, organic material and biomass. Sludge is typically produced by biological waste treatment, but also includes accumulated solid wastes from other types of deoiling equipment and hydrocarbon and water emulsion sludges. The handling and treatment of emulsion sludges is addressed in more detail in the current SlPM Dehydration/Deoiling manual (EP 89-0150, section 5.7, due to be updated). However a number of the sludge treatment processes presented in the following discussions may also be applied to emulsion sludges. The potential significance of sludge streams should not be underestimated. They may contain concentrated levels of environmentally significant components such as hydrocarbons, heavy metals and radionuclides and may be subject to special environmental regulations. Adequate provision must be made for the removal, handling, storage and treatment of solid and sludge waste products at the design stage. Table 4.5 summarises the various treatment stages that can be applied to sludges. Depending on the application, a sludge treatment process may utilise all or only some of these stages. Each unit operation is briefly addressed in the following discussions. The "Sand Wash Design Manual'' EP 93-1270, due to be issued in the 4th quarter of 1993, contains additional information on the handling and treatment of accumulated solids.
4.5.3.2.
Stabilisation Stabilisation is the treatment stage designed to convert the sludge to a safe and stable state. This involves the breakdown of degradable organic material to discourage microbial growth (putrescibility control) and to reduce the levels of micro-organisms to minimise any threat of pathogens.
A number of biological and chemical processes can be used to stabilise the sludge. Stabilisation can also be used as a means of reducing the volume and weight of sludge.
4.5.3.3.
Conditioning Conditioning is designed to improve the dewatering characteristics of the sludge. Chemical conditioning includes the use of coagulation and flocculation chemicals to form larger, more readily separated agglomerations of solids. Elutriation is a washing stage that can be used before chemical conditioning to improve the effectiveness of the chemical treatment. Heat treatment can break down the structure of the sludge, resulting in a more easily dewatered sludge.
4.5.3.4.
Concentration Concentration of the sludge often precedes dewatering to reduce the volume of sludge to be dewatered.
SlPM Deoilinl: M(r111ra1. EP 93-1315. Rev 1.1. Nov 1993, File minw = 4CIIAP.DOC
PuKe 4- 7
4. Water disposal
Concentration can be achieved by gravity thickening, dissolved air flotation or centrifuging, with gravity thickening being the most common method, The concentrated sludge underflow from a gravity thickener would typically contain in the order of 8 to 15% solids by volume.
4.5.3.5.Dewatering
Sludge dewatering removes sufficient water from the sludge to form a damp solid or sludge cake. A range of processes are available, including centrifuging, filtration, drying beds and drying lagoons. Centrifuges can typically achieve a dewatered sludge of 25 to 40% volume solids, while filtration can typically achieve 40 to 60% volume solids. A vibrating membrane has also been developed for dewatering sludges.
4.5.3.6.Drying
Drying of a sludge typically takes the form of heat treatment to produce a relatively dry sludge with a water content of only 8 to 10%. Incineration is a more extreme form of drying where the combustible elements of the sludge are converted to combustion products. Incineration will still leave some sludge residue in the form of ash which will still require a suitable form of disposal.
4.5.3.7.Residual disposal
Any sludge handling system must include a method for the disposal of final residues. The most common methods of disposal are sanitary land fill, application on agricultural land and deep well injection. Land farming of sludges can be particularly effective in tropical regions. Residual disposal will usually require suitable facilities for the handling, storage and transportation of the residue.
Table 4.5 Sludge treatment unit operations Unit operation Stabilisation Methods Aerobic or anaerobic digestion Chemical stabilisation Composting Heat treatment Irradiation Lagooning Chemical addition Elutriation Heat treatment Centrifuging Dissolved air flotation Gravity settling Centrifuging Drying beds Lagoons Filtration Chemical fixation Land application/farming Land fill Well injection Function Putrescibility control Pathogen destruction Odour control Volume and weight reduction Gashy product production Improve dewatering Improve solids capture Improve processing rate Thickening Water removal Blending of sludges Water removal Volume and weight reduction End product utilisation Disposalto waste End product utilisation
;orbitt, R.A., ISBN 0-07-013158-9,
Residual disposal
Pup? 4-8
SIPM Droilinh. Mwuol. EP 93-1315, Rrv 1.1, Niiv 1993, File ncirnr = 4CHAP.DOC
.....
5.1.
GENERAL
A waste water stream is a complex mixture of constituents, both dissolved in the water and present in the dispersed hydrocarbon phase. In addition to the liquid phases, gas and solid phases may also be present. In E & P operations, most routine samples of effluent water are taken for the determination of hydrocarbon content. For this analysis, the most important consideration is obtaining a representative sample of the dispersed hydrocarbons. A representative sample is required to ensure; Accurate measurement of the overall hydrocarbon content. An inaccurate measurement indicating a high hydrocarbon concentration may have implications in meeting regulatory effluent quality standards. Effective process design and operation. The accurate measurement of hydrocarbon concentration and droplet size distribution of the dispersed phase is critical for the correct selection, design and operation of deoiling equipment. Because of the potential complexity of a waste water effluent stream, and the regulatory significance of the results of waste water analysis, it is important that there is a clear understanding of the factors associated with sampling that may influence the results of subsequent analysis procedures. The importance of following good sampling practices cannot be understated. Laboratory analyses, operational decisions, process and equipment design and environmental protection are all activities of which sampling forms the first step. Poor sampling degrades the value of these subsequent activities. At the very least, poor sampling wastes time and effort as repeat samples are required to confirm uncertain results. The procedures discussed in this section are designed for the sampling of waste water streams. For the sampling of well stream fluids (oil, gas, condensate etc.) the user is referred to "Guidelines for manual sampling and analysis of hydrocarbon fluids", SIPM EP 92-0980. A number of references are made to ASTM standard methods (American Society for Testing and Materials). These standards are readily available through most technical library services or can be requested from SIPM.
5.2.
5.2.1.
d d
Sample points should preferably be located in a region of turbulent flow. The transition to turbulent flow starts when the Reynolds number is greater than 3000. Sample points.should be at least 3 pipe diameters downstream and 1 pipe diameter upstream of any flow disturbance such as a bend, pump, manifold etc. (ASTM D 4177-82, Ref.l.07.1 .c). Sample points should preferably be located in vertical sections of piping where the fluid flow is upwards. The fluids in vertical piping are not subject to phase separation and stratification due to gravity. Sample points should be located both immediately upstream and downstream of the deoiling equipment with no potential shear sources (e.g. control valves) between the deoiling equipment and the sample point. Sample points should provide an effective and safe means for the collection and disposal of the fluid flow required to flush the sample point. Sample points should not be located on or immediately after bends or other flow disturbances. Forces exerted on the fluid by flow disturbances (particularly bends) will result in a separation of phases of different densities.
d
d d
%
SIPM Droiliitx Monitril, EP 93-1315, Rcv 1.1. Nov 1993. File ii(iiiir = SCIIAP.DOC
Pup2 5- 1
Effective operation and trouble-shooting of deoiling operations can only be performed with the provision of adequate sampling points both upstream and downstream of all stages of deoiling equipment. Designs for new facilities should always be reviewed for the provision of sufficient and suitably sited sampling points. In some cases, legislation may specify a particular sampling location for the monitoring of effluent water streams before discharge into the environment. Such a sample point may be required in addition to the sampling points required for the normal monitoring and control of deoiling equipment.
5.2.2.
4 4
%
Sample points should always use a sample quill to ensure a representative sample. The sample quill should preferably extend to the centre of the pipe or at least a distance of D/3 away from the piping wall (Ref.l.07.1 .n).
If sampling from horizontal piping cannot be avoided, samples should not be taken from the top or bottom of piping. The sample quill should be installed either to allow sampling from the centre of the pipe or at a point along the line of the "nine o'clock'' or "three o'clock'' positions.
5.2.3.
The first design has the end of the sampling quill bevelled at 45".This is a cheap and relatively simple design. The second design uses a curved end to smooth the flow path into the sample quill. Both designs have the advantage of being straight which allows the quill to be inserted in a slim fitting similar to a thermowell and allows the probe to be easily withdrawn as required for maintenance. The sample point design illustrated in Figure 5.2 has a long radius bend designed to minimise any
5-2
SlPM Droilinl: Miuiitctl. EP 93-1315. Rrv 1.1. Nov 1993, File nume = 5CHAP.DOC
P(J#C
HIJOZb16P
The following guidelines should be applied to all sample quills. The wall thickness of the quill should be as thin as possible and the tip of the quill should be bevelled to a sharp edge. With a blunt edged quill a damming effect can occur upstream of the tip, deflecting droplets away from the quill. As previously mentioned, the quill should preferably extend to the centre of the pipe or at least a distance of D/3 away from the piping wall. However the length of the quill may be restricted by the need to withstand the mechanical forces exerted by the flow in the pipe. A procedure for determining the maximum length of a sample quill is given in Standard Practice for Automatic Sampling of Petroleum and Petroleum Products, ASTM D 4177-82 (Ref.l.07.1 .c). Care must be taken to ensure that the quill is installed with the opening facing in the upstream direction. The sample quill should be fabricated with an integral labelled tab to ensure correct orientation. The internal diameter of the sample quill must be sized to allow an isokinetic fluid velocity through the quill while ensuring the volumetric flow rate is within the capacity of the sampling equipment. Section 5.5.2 discusses isokinetic sampling in more detail.
5.3.
SAMPLE CONTAINERS
Materials
5.3.1.
5.3.1.1, Glass
Glass sample containers are suitable for most water analyses. Glass sample bottles are preferred for non-routine samples, especially for the determination of heavy metals or when the sample will not be analysed immediately. The use of dark glass bottles will reduce photo-degradationof the sample. However, glass sample containers should not be used for samples from which small quantities of hardness, silica, sodium or potassium are to be determined.
5.3.1.2.
Plastics
High density linear polyethylene, polypropylene and Teflon containers are suitable for most water analysis duties. However users should be aware that these containers are slightly permeable to light volatile hydrocarbons and gases such as carbon dioxide. Mercury will also be lost from the sample through the walls of the sample container. Plastic containers are acceptable for routine determination of hydrocarbon content of water samples, as errors introduced by sampling considerations will far outweigh potential errors from sample container materials. However glass sample containers should preferably be used for non-routine analyses, heavy metal analyses, or when samples will not be analysed immediately.
Niiv
199.3. File
i i i i i ~ i e=
SC//Af.DOC
Puxe 5-3
5.3.2.
The cleaning steps consist of an initial wash with a warm aqueous detergent mixture followed by six hot tap water rinses, two rinses with reagent water, a rinse with reagent grade acetone and a final rinse with solvent such as pentane, hexane, cyclohexane, dichloromethane, or chloroform followed by drying in a clean oven at 105C or hotter for 30 minutes. If the glassware requires cleaning under field conditions, it should be washed with warm aqueous detergent followed by extensive water rinsing. A solvent rinse with acetone should be made, if possible, followed by a lengthy air drying to remove residual solvent
More stringent cleaning procedures for both plastic and glass sample containers can be found in ASTM D 3694-92, Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents (Ref.l.07.2.b). Sample containers for determination of trace substances such as heavy metals will require an even more thorough cleaning procedure. A typical procedure taken from the Thornton Research Centre (Ref.1.02.2.d) is as follows;
Sample containers are cleaned by standing overnight at room temperature containing 1:l hydrochloric acid. The containers are then rinsed clean with de-ionised water and allowed to stand overnight at room temperature containing 20% v/v nitric acid. The containers are finally thoroughly rinsed clean with de-ionised water, then stored in a particle and fume free environment prior to dispatch. Acids used should be analytical reagent grade.
5.4.
I
I
I Droplet size distribution must not be altered by Simply ensure isokinetic conditions are followed
at the point the sample enters the sample quill. This ensures a representative sample enters the sample system.
Reference section 5.5 the sampling. lsokinetic conditions to be followed where the sample enters the sample quill with neutral behaviour in the remainder of the sample system. Reference section 5.6
Routine Sampling
Puge 5-4
SlPM Deoilinl: Mnnucrl, EP 93-1315, Rev 1.1. Nov 1993, File nume = 5CHAP.DOC
It should be noted that for both routine sampling and sampling for the measurement of droplet size distribution, to ensure a representative sample enters the sample system;
0
A sample quill should be used. lsokinetic conditions should be maintained in the sample quill itself.
5.5.
ROUTINE SAMPLING
Introduction
The concentration of contaminants in effluent waters is often very low. The concentration of mineral hydrocarbons in effluent waters is generally lower than 40 parts hydrocarbon per million parts water (typical offshore effluent specification) while the concentration of other contaminants such as heavy metals is typically a thousand times lower, in the order of parts per billion. Due to these low concentrations, careful sampling practices are required to ensure samples of effluent water are representative and not contaminated.
5.5.1.
5.5.2.
lsokinetic conditions
lsokinetic sampling is simply achieved by ensuring that the velocity of the sample in the sampling quill is equal to the velocity of the fluid in the process line being sampled. This is critical when sampling streams containing a dispersed phase such as hydrocarbon droplets or suspended solids.
L
O
* =
-/------
- 0
Vsarnple
Visokinetic
Vsarnple = Visokinetic
Vsarnple
> Visokinetic
Figure 5.3 Effect of sampling under isokinetic and non isokinetic conditions
Figure 5.3 illustrates the influence of the sampling velocity at the tip of the sampling quill. When not sampling at the correct isokinetic velocity the disturbance in the flow profile can result in a bias in the sampled size distribution due to the different inertial properties of the various sized elements of the dispersed phase. lsokinetic sampling is only effective when a sampling quill is used. Sampling from a simple side mounted sample point will introduce large changes in the flow profile which will tend to bias the sample whether or not isokinetic conditions are followed. For consistency isokinetic conditions should be used when sampling from a side mounted sample point, however to ensure a representative sample a sample quill should be fitted.
To determine the isokinetic sampling rate, the velocity of the fluid in the main process line should be calculated. Then, knowing the internal diameter of the sample quill, the appropriate volumetric sampling flow rate can be calculated which will result in the same fluid velocity in the sample quill as in the process line. The sampling flow rate for a non-hazardous water stream would usually be simply measured by timing the filling of a known volume (bucket and stop-watch technique).
Table 5.1 gives an indication of the typical sampling rates required to achieve isokinetic sampling through different sized sample quills, based on an typical flow velocity of 2.5 m/s in the process line being sampled. Figures 5.5 and 5.6 at the end of this chapter can be used to quickly determine the
SlPM Deoilir~gMiiniral. EP 93-1 715, Rev I 1. Nov 1993. File m r i i i c = SCIIAP DOC
Puxc 5-5
&diameter
(mm)
Sampling quill
Basis: Assumes 2.5 m/sec fluid velocity in process line. Inside diameters correspondto schedule 40 pipe with 3/8",1/2", 3 4 " and 1' nominaloutside diameters .
32 20 12 7
I
5.5.3.
5.6.
5.6.1.
POKC 5-6
SIPM Deoilinp Momctrl. EP 93-1315. Rrv 1.1, Nirv 1993, File ncrmr = 5CHAP.DOC
5.6.2.
5.6.3.
5.6.3.1.
5.6.3.2.
Pressurised sampling Where the droplet size distribution is to be measured, sampling should be conducted using a pressurised sampling method. Figure 5.4 illustrates one such sampling technique using a flow-through sample bottle. The sample quill should be sized to achieve isokinetic conditions at the point where the sample enters the sample system, however the remainder of the sample piping should be sized to achieve neutral conditions. Isolation valves should be full bore valves to minimise shear and the flow rate through the sample bottle should be regulated by using the downstream needle valve.
w Needle valve
~~
iiiiiiie
= SCIIAP DOC
PuRe 5-7
5.6.3.3.
Depressurisation Both the atmospheric and pressurised sampling methods discussed above eventually depressure the sample. This depressurisation is required by some analytical equipment for the measure of the droplet size distribution. However, depressurisation may lead to the generation of gas bubbles which may have a number of detrimental effects such as; Interference with the method used to measure the droplet size distribution e.g. by obscuration or optical interference. Gas bubbles may be registered as dispersed droplets. Gas bubbles generated within a dispersed droplet may shear the droplet as they evolve, altering the droplet size distribution.
If gas evolution may be a problem, droplet size distributions should be measured at process conditions without depressurisation using either the KSLA microphotograph technique or the GalaiNortoil particle/droplet size analyser (see chapter 6).
5.7.
5.7.1.
Introduction
After sampling, a sample will tend to age through the action of chemical and biological reactions. This ageing will tend to alter the composition and character of the sample and thus should be prevented or minimised. Samples should preferably be analysed or utilised immediately to minimise the effect of ageing. However when this is not possible, appropriate storage and preservation techniques should be used to extend the representative life of the sample. Brief summaries on sample preservation and storage are given in the following discussions. Additional information can be obtained from the following references,
0
Standard Practice for the Preservation of Waterborne Oil Samples, ASTM (Ref.l.07.2.a).
3325-90
Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents, ASTM D 3694-92 (Ref.1.07.2.b). Standard Practice for Estimation of Holding Time for Water Samples Containing Organic
SIPM Denilinp Mii/iwi/,EP 9.1-1315, Rev I . I , NOV1993. File nomr = 5CliAP.DOC
Puae
5-8
5.7.2.
Chemical Preservation
The life of a sample can be extended by the addition of preservative chemicals to the sample. These chemicals inhibit the chemical and biological changes that may alter the composition of the sample over time. The most common preservation technique used is the acidification of samples which are to be analysed for hydrocarbon content. Acidification (typically using hydrochloric acid) to a pH <: 2 will inhibit the biological degradation of organic materials. Different preservation chemicals may be required for the preservation of other components of the sample. In some cases separate samples using different preservation chemicals may be required.
5.7.3.
Sample storage
To maximise the storage life the sample should be stored in dark glass bottles in a dark area to minimise photo-degradation of the sample. Storage at a temperature of approximately 5C will inhibit biological and chemical reactions. Freezing should be avoided, especially for emulsions where the inter-facial film may be destroyed by the formation of ice crystals. Air, or more specifically oxygen, should be excluded from the sample to prevent oxidation reactions. Air may be displaced from sample containers using a relatively inert gas such as nitrogen.
. )
ID=26.6mm
1
ID=20.9mm
_. 0)
-0
.2 2.0
E. a
3
3 . 0
1.0 -
ID=12.5mm
0.0
60.0
E: ln
0)
50.0
n
1 -
_ .
5 30.0
c
2
m
40.0
; F
g! .3
'0
20.0
i =
0-
g!
10.0
0.0 0.00
0.50
1.oo
1.50
2.00
2.50
3.00
3.50
4.00
Figure 5.6 Time required to fill a 10 litre container while sampling under isokinetic conditions through different sample quill inside diameters (Inside diameters correspond to schedule 40 pipe with 3/8", 1/2", 3/4" and 1" nominal outside diameters)
P U ~5CIO
SIPM Droilinx Mitnuitl, EP 93-1315, Rev 1.1. Niiv 1993. File nome = 5CHAP.DOC
6.1.
GENERAL
For most E & P deoiling operations, two of the most important characteristics of the water stream are the concentration of the dispersed and dissolved hydrocarbons and the size distribution of the dispersed hydrocarbon phase. Infrared absorption analysis is the most common procedure for determining the concentration of hydrocarbons in waste water and the advantages and limitations of this method of analysis are presented in this chapter. Of particular importance is the recognition of the following potential limitations in many infrared analysis procedures; The absorption frequencies used may not be sensitive to the presence of aromatic hydrocarbons. The standard procedures do not differentiate between dispersed and dissolved hydrocarbons. The accuracy of the measurement is dependent on the use of suitable calibration samples. Infrared adsorption analysis is discussed in detail in section 6.2. However other methods of analysis are also available and these are briefly discussed in section 6.3. On-line oil-in-water monitors are discussed in section 6.4. The size distribution of the dispersed hydrocarbon phase is one of the most important parameters governing the performance of most deoiling equipment. The measurement of droplet size distributions is discussed in section 6.5.
6.2.
6.2.1.
Introduction
The most common method of measuring the concentration of hydrocarbons in water is infrared absorption. This method is based on the absorption of infrared light by the carbon-hydrogen (C-H) bonds present in hydrocarbons. The procedure generally consists of the following steps. Sample preservation and preparation. Extraction of the hydrocarbons from the water using an organic solvent. Conditioning of the extract to remove solids, water and polar hydrocarbons. Measurement of the infrared absorption at one or a number of infrared light wavelengths. Standard infrared analysis procedures measure the total quantity of hydrocarbons extracted from the water by the solvent and make no distinction between dispersed and dissolved hydrocarbons. Table C.l and C.2 in Appendix C summarise the key characteristics of 15 published procedures for the determination of hydrocarbons in water. It should be noted that the results obtained from infrared analysis are not an absolute measure of the hydrocarbon content of effluent waters, but are calibrated against reference standards. Inappropriate calibration standards will result in an inaccurate determination of hydrocarbon content. In particular, the aromatic content of effluent samples may be excluded from the analysis due to inappropriate calibration standards or the use of infrared wavelengths which are not absorbed by the carbon-hydrogen bonds present in aromatics. In addition, many infrared analysis procedures do not measure polar hydrocarbons which are removed from the sample before analysis. This includes both polar hydrocarbons derived from the well-stream (organic acids and phenols) and polar process chemicals such as methanol and glycols. It should be noted that infrared hydrocarbon analysis is only a relative determination of hydrocarbon content in water. When a more complete breakdown of the hydrocarbons present in the effluent waters is required a more absolute method of analysis such as gas chromatography must be used.
6.2.2.1.
Acidification
If the sample is not to be analysed immediately, it is common practice to acidify the sample. Acidification has the following beneficial effects;
Minimises hydrocarbon losses due to biological degradation. Improves phase separation by countering the presence of alkaline based emulsion stabilisers. Dissolves any precipitated calcium carbonate. Hydrochloric acid is typically used to avoid potential precipitation problems that may occur with anions from other acids (e.g. sulphates from sulphuric acid). ASTM D 3694-92, Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents (Ref.l.07.2.b), recommends acidification to a pH i2 to inhibit biological activity for biodegradable organic chemicals. Acidification has a potential problem in that it may change the dissociation equilibrium of weak organic acids. These liberated organic acids would then be detected by the subsequent hydrocarbon analysis and incorrectly reported as part of the hydrocarbon component of the water. This problem can be avoided by ensuring that after the organics are extracted from the water phase, the extract is passed through a suitable polar absorbent. As the liberated organic acids are polar, they will be removed by the absorbent and will not be measured as part of the mineral hydrocarbon content of the water.
6.2.2.2.
Gas purging
The Paris Commission (Parcom) guidelines governing water discharges from offshore platforms in the North Sea allows samples to be purged with a nitrogen gas flow (at approximately 1 litrehin) for a period of 45 seconds at a temperature of 30C. The justification for this gas purging is to remove light components that would normally flash into the gas phase on discharge into the environment, leaving only the hydrocarbons that will remain in the aqueous environment. However gas purging will also strip volatile hydrocarbons from the sample. Up to 75% of the BTEX aromatics may be stripped by this purge, resulting in an underestimate of the hydrocarbon content of the effluent stream.
6.2.3.
Hydrocarbon extraction
6.2.3.1.
Selection of solvent
After sample preparation the hydrocarbon content of the water is extracted using a solvent. Carbon tetrachloride (CCI,) and Freon 113 are the two most commonly used solvents, however both are being phased out of use. Carbon tetrachloride requires careful use to ensure occupational health safety. Freon 113 is one of the CFC chemicals recognised as harmful to the ozone layer and under the Montreal Protocol must be eventually phased out of use. A number of alternative solvents could potentially replace the currently used solvents, though none of the alternatives has been officially accepted for infrared analysis. The following reference discusses the use and performance of range of alternative solvents.
A protocol for determining oil and grease in produced waters, Simms, K., Zaidi, A., Bhargave, O., 1992 International produced water symposium, San Diego, Feb 4-7 1992. Reprinted in Produced Water, edited by J.P. Ray and F.R. Engelhart, Plenum Press, NY, 1992. Available from SlPM on request (Ref.l.02.1 .a).
An alternative is the elimination of solvent altogether. Manufacturers are developing infrared absorption, ultraviolet absorption and ultraviolet fluorescence techniques that can be applied directly to the water sample without the use of a solvent. KSEPL are also in the process of developing a direct infrared absorption method. The primary aim of these developments is application as on-line oil-in-water monitors and commercial units are currently available. However when tested, the performance of these units has typically not been satisfactory and at this stage these methods cannot be considered as suitable replacements for the current solvent extraction based methods.
PlI,qc! 6-2
SlPM D e i i i l i i i ~Miiiiucil. El 93-1315, Rev 1.1, Niiv 1993, File iiime = 6CHAP.DOC
6.2.4.
6.2.5.
6.2.5.1.
Infrared analysis
Basis of measurement Infrared analysis is based on the absorption of infrared light by the C-H bonds present in hydrocarbons, with the absorption being related to the concentration of hydrocarbons. The solvent extract obtained from the previous procedures is scanned over a range of infrared light wavelengths in an infrared spectrophotometer. The absorption at characteristic wavelengths is related to the presence of particular C-H bonds as illustrated in Table 6.1. The presence of any of these groups will result in some absorption, hence the need to remove polar hydrocarbons before the absorption is measured. Similarly, the solvent used for the hydrocarbon extraction must be selected on the basis of not contributing to the infrared absorption, hence the use of halogenated solvents. Many infrared analysis procedures only measure absorption for the CH, group (see Table C2 in Appendix C). This is generally satisfactory as this is the most common carbon-hydrogen group present in mineral oils. However, aromatic hydrocarbons consist largely of CH bonds. If the absorption is not measured at the wavelength absorbed by these bonds (3.30 pm), these compounds will not contribute to the absorption and may go undetected (though this also depends on other factors such as the composition of the calibration sample). This could lead to a underestimate of the hydrocarbon content in effluent waters,
(11171)
CH CH3
m-5
3030 2959 2924 2857
Characteristic
Low molecular weight aromatics Saturated hydrocarbons Long straight chain saturated hydrocarbons and cycloalkanes Long straight chain saturated hydrocarbons and cycloalkanes
6.2.5.2.
Calibration Once the absorption of the extract has been measured it must be converted into the required analytical measurement. This is achieved by comparison with the absorption measured for a known oil or reference oil calibration sample. Known oils Known oils are calibration samples made by mixing water with known quantities of a hydrocarbon sample taken from another part of the process. A typical source for the known oil may be the hydrocarbon reject stream of a water treatment package. Such known oils may not be completely representative of the hydrocarbons present in the effluent sample, especially if the water treatment system has additional separation stages after the point where the known hydrocarbon is obtained. The known oil may also be subject to a degree of "weathering" which may alter its absorption. However, in general, known oils are likely to be more representative of the actual hydrocarbons in the sample than the alternative calibration methods. Reference oils Reference oils are calibration samples made by mixing known quantities of a defined mixture of hydrocarbons. As an example, the reference oil defined by the Netherlands NEN 6675 standard consists of 37.5% iso-octane, 37.5% cetane and 25.0% benzene. The inherent drawback in the use of a reference oil is that if the composition of the hydrocarbons in the effluent stream is significantly different to that of the reference oil the accuracy of the hydrocarbon measurement will be reduced. The absolute accuracy of the method will also be reduced if the hydrocarbons in the sample contain a significant fraction of fully substituted carbon atoms i.e. carbon atoms with no C-H bonds. These fully substituted carbons atoms will not contribute to the absorption and thus will not be accounted for unless the reference oil used also contains a similar proportion of fully substituted carbon atoms. The advantage of reference oils is that they may be specified as part of standard method, allowing the same reference mixture to be used consistently in different locations. This at least provides a consistent basis for comparison of results from different locations and allows for the checking of procedures by independent authorities. However the accuracy of the result will be lower due to the variation between the actual hydrocarbons in each sample and the hydrocarbons in the reference oil. Soecific absorDtion coefficients An alternative to using calibration samples is the use of specific absorption coefficients. These coefficients can be built into equations which relate the measured absorption directly to the hydrocarbon content. As with use of a reference oil, the disadvantage of this process is that it assumes the composition of the
PU,qC
6-4
6.2.5.3. Results
Units of measurement The concentration of hydrocarbons present in water should generally be expressed using the unit of mg/l. The basis for the ppm unit (parts per million) is often poorly (or not) defined and could be interpreted as either a volume or mass basis. In some cases, legislation may require the reporting of results in alternate units such as mg/kg, ppm(w) or ppm(v). Accuracv
It can be seen from the discussions above that the accuracy of measuring the concentration of hydrocarbons in water will be dependent on a number of factors:
Obtaining a representative sample. The effectiveness of the extraction stage. This is in turn governed by factors such as the solubility of the hydrocarbons in the chosen solvent, the method and period of agitation used during extraction, then number of extraction stages and the effective separation of the solvent from the water phase. The potential loss of hydrocarbons during the removal of polar hydrocarbons from the extract. The measurement of the absorption at suitable wavelengths. The suitability of the calibration method. The accuracy of the method is generally reported to be in the order of +looh.
6.3. 6.3.1.
6.3.2.
Gravimetric analysis
A solvent is used to extract the hydrocarbon content from the effluent sample. The extract is filtered to remove solids, water and salt, then evaporated under standard conditions to leave a residue. The residue is weighed and is reported as the hydrocarbon content. Gravimetric analysis tends to underestimate the concentration of hydrocarbons in water due to the loss of lighter hydrocarbons during the evaporation procedure. Comparative trials indicate that the gravimetric method may measure a hydrocarbon concentration in the order of 20% lower than infrared analysis (Ref.l.02.1 .a). This agrees with a 20% variation measured at a Shell crude oil terminal (Ref.2.05.2.e).
6.3.3.
It is not normally necessary to filter, dry or pass the sample through an absorption column.
The method is simple, cheap and portable and suitable for use under difficult conditions. However, the method may have a tendency to underestimate hydrocarbon content as the coloured components in crude oil are very easily absorbed onto surfaces and may be lost.
6.3.4.
Gas chromatography
The hydrocarbon content of the effluent sample is extracted with a suitable solvent and injected into a gas chromatography column which separates hydrocarbons in order of boiling point. Gas chromatography gives a detailed analysis of the composition and may be applied for special studies, but is generally too time consuming for routine use. are not detected The main disadvantage of this method is that high boiling point components (>300"C) as they are not carried through the column. The sensitivity of the method is O.lmg/l for oil, for single components less than 0.01 mg/l.
6.3.5.
Others
A range of other methods can be used for determination of hydrocarbon content, particularly in trying to measure hydrocarbon content on-line without solvent extraction. Infrared light scattering and ultraviolet absorption methods have been used for on-line instruments which are discussed in more detail in section 6.4 and Appendix D.
6.3.5.1.
Ultraviolet absorption Aromatics and other compounds with conjugated or pseudo-conjugated double bonds will absorb UV light. If the typical concentration of these particular hydrocarbons is known, the UV absorption can be related to the overall hydrocarbon content. Dual wavelength UV beams are sometimes used, the first measuring the absorption of the aromatics and the second acting as a reference to compensate for fouling and turbidity.
6.3.5.2.
Ultraviolet fluorescence spectrometry Aromatics and other compounds with conjugated or pseudo-conjugated doubfe bonds will also fluoresce when exposed to suitable ultraviolet light. The fluorescence can be related to the hydrocarbon content of the effluent sample.
6.3.5.3.
Concentration derived from droplet size analysis Dispersed oil-in-water takes the form of discrete oil droplets suspended in the continuous water phase. If the number and size of the hydrocarbon droplets is known, the volume of hydrocarbon in the water sample can be determined by calculating the cumulative volume of the hydrocarbon droplets. Knowing the average density of the dispersed hydrocarbons present allows the total hydrocarbon concentration to be calculated. Ultrasonic oil-in-water monitors operate on the basis of recognising the presence of dispersed droplets. An ultrasonic signal is reflected back by dispersed hydrocarbons in the sample to give an indication of the hydrocarbon content. The result will be affected by the droplet size, therefore the sample must be homogenised before analysis. Droplet size analysers are available which allow continuous on-line measurement of droplet size
Pup? 6-6
SIPM Droilii1X Mirnrrtrl. EP 93-1315, Rev 1.1. Nov 1993, File n o i w = 4CHAP.DOC
6.4.
6.4.1.
General
The development of an on-line oil-in-water monitor has been pursued by a number of manufacturers. Continuous measurement of the hydrocarbon content in the effluent waters from production sites would have the following potential benefits. More rapid detection of excess hydrocarbon content in effluent discharges. More feedback on the operation of deoiling equipment, promoting improvements in operational procedures and equipment design. Minimisation of manual sampling and analysis requirements. A range of commercial oil-in-water monitors have been tested by KSEPL and in trials at the Orkney Water Test Centre (OWTC). Although some of the meters tested have shown potential, at the time of testing none could be recommended as suitable for continuous operation in an operating environment. However, it should be recognised that the suitability of continuous oil-in-water monitors is often gauged on their absolute accuracy and their potential to replace current sampling and analysis procedures. Although commercial monitors may not yet be suitable for this purpose, their use in less rigorous applications should not be overlooked. Commercially available monitors could potentially be used in the following applications: To give a continuous indication of relative deoiling performance, calibrated by continued routine sampling and analysis. To act as an alarm, indicating when significant excursions occur in effluent hydrocarbon levels. This would facilitate more rapid corrective action, minimising the potential impact on downstream processes or the discharge environment.
A third series of oil-in-water monitor trials is to be conducted at the OWTC in the second half of 1993.
Table 6.2 lists the range of oil-in-water monitors that have been recently tested. The relevant reports are referenced in the Bibliography and the results from the OWTC trials have been summarised in Appendix D. Full copies of the reports are available from SlPM EPD/421 on request.
Table 6.2 Recently tested oil-in-water monitors Oil-in-water monitor tested Bristol Babcock OCD-30 Facet Mark Vlll Bilge Alarm Horiba OCMA-25 Monitek Micro-Pure MPS-D Pure Alert Oili-S Type 300 Schlumberger Oilcon EJB5l Teledyne 661R Fluoritest-S OCD-37 Oili-S Mark 1000 C Turner Model 10 Baird Petrolarm Horiba Ocma 25 Tested by OWTC - Phase I OWTC Phase I OWTC Phase I OWTC - Phase I OWTC - Phase I OWTC - Phase I & Phase II Report date March 90 March 90 March 90 March 90 & October 91 March 90 March 90 & October 91 March 90 October 91 October 91 Aug 90 8 October 91 October 91
OWTC - Phase II
Nov 88
May 84
6.5.2.
Sampling
The droplet size distribution of a dispersed hydrocarbon in water is constantly changing as a result of the emulsification and coalescing forces acting on the fluid. To accurately measure the droplet size distribution a careful sampling procedure must be followed. Sampling must be conducted to ensure; That the sample is representative. Obtaining a representative sample of a two phase liquid can be very difficult and a number of samples may be required with the results averaged. The sample point is correctly designed with a quill extension into the main fluid flow away from the piping wall. In some cases samples may be required at different points to ensure that the droplet distribution does not alter over the cross-section of the area being sampled (e.g. stratified flow). That iso-kinetic sampling is used at the point where the sample enters the sample system. This ensures the sample is not biased by changes in the flow profile. That iso-energetic conditions are maintained after the sample has entered the sample system. This will ensure that sampling does not alter the droplet size distribution by changing the dynamic equilibrium between coalescence and emulsification. Depressurisation of the sample should be avoided. Depressurisation is likely to alter the droplet size distribution through the imposition of shear forces on the sample and may lead to problems due to the evolution of gas bubbles. Appropriate procedures for sampling to determine droplet size distribution are discussed in detail in section 5.6.
6.5.3.
6.5.4.
Others
Visual imaging of the dispersed hydrocarbon droplets is also available as an option with the VortoiEalai particle size analysers. A visual image of the dispersed droplets or solids is obtained using a CCD video camera microscope. The resulting image is not directly used for determining size distribution, however the image is be analysed for shape based criteria such as area, shape factor and aspect ratios and can be used to give a visual impression of the droplets and particles being measured. This method has the advantage in that the image is obtained from a flowing sample, not requiring the sample to be isolated or requiring the droplets to settle. The sample cell is rated for pressures up to 40 barg allowing for the size analysis of many streams at process temperatures and pressures. Other alternative image analysis services similar to the KSLA method are offered by independent companies. Examples include Quantimet, Joyce-Loebl, SCIL, TIM etc. Additional details can be obtained from KSLA, EE/4.
6.5.5. 6.5.5.1.
OWTC trials
A selection of particle size analysers were tested at the Orkney Water Test Centre over the period of November 1990 to February 1991. The following report was issued and is available from SIPM EPD/421 on request. Particle size analyser trials conducted at the Orkney Water Test Centre November 1990 - February 1991, Tullock, S.J., Oct 1992, EP-No.92-1952 The name, basis of operation and sample condition of the particle size monitors tested is listed in Table 6.3. A more detailed summary of the results from the trial is included in Appendix E.
Table 6.3 Particle size analysers tested at OWTC Particle size analyser Coulter LS130 Coulter Multisizer Vortoil/Galai CIS1002 Lasentec Partec 250 Malvern Mastersizer Basis of operation Laser diffraction Aperture counting Laser time of transition Forward scattering Laser time of transition Backward scattering Laser diffraction Sample Condition
-~
Batch, sample depressurised Batch, sample depressuhed, sample dilution may be required. Continuous, at process conditions up to 40 barg. Continuous, analysis probe can be directly inserted in process piping up to 10 barg. Batch or continuous, sample depressurised
6.5.5.2.
Pu,qe 6-10
SIPM Droiliiix Mor~itcrl. EP 93.1315, Rrv 1.1. Nov 1993, Filr nctmr = 6CHAP.DOC
7.1.
INTRODUCTION
In many installations, the majority of design or operating effort is concentrated on the hydrocarbon producing systems with only relatively brief consideration given to the waste water treatment system. In particular, water treatment facilities are often regarded as "end of pipe" solutions to a water treatment "problem".
A preferable situation is where water treatment is considered as an integral part of the total process design. Integration of water treatment equipment into the overall process system will result in a more efficient and cost effective facility.
Dehydration and deoiling processes should be considered as a single system with the emphasis on complementary design. Examples where such integration has brought improvements in operation include;
0
Minimisation of shear and promotion of coalescence in flow lines, pipe lines and piping systems upstream of dehydration has improved the quality of both oil and water outlet streams. The use of plate packs in primary separators to improve the quality of both oil and water outlet streams.
A gaskondensate installation with hydrocyclones operating at a high separator pressure (circa 120 barg) to minimise droplet shearing. A gashondensate installation designed to avoid the use of corrosion inhibitors (which stabilise small hydrocarbon droplets) and with the gashquid separator designed for effective three phase separation at high pressure.
The use of continuous dehydration designs in preference to batch dehydration has resulted in more consistent and stable feed streams to downstream water treatment equipment and more efficient water deoiling. These examples highlight the potential benefits that may be achieved by adopting a system approach to the design of the overall production facilities, particularly the dehydration and deoiling processes. This philosophy is examined in more detail in the following discussions. Section 7.2 presents guidelines to assist the user in effective process design and equipment selection for water treatment systems, while section 7.3 discusses overall system optimisation and integration considerations.
7.2. 7.2.1.
7.2.2.
4.
NTiFY UPSTREAM PR COULD COMPLICATE THE WATER TREATMENT AND WHAT STEPS CAN BE TAKEN TO MAKE THE WATER EASIER TO TREAT
7.2.3.
A suitable disposal route for the treated water should be identified. Both surface and subsurface disposal
options should be considered. Health, Safety and Environmental considerations should take first priority in the setting of treated water quality requirements. This also applies to sub-surface disposal as it is possible for water disposed into some subsurface structures to migrate to the surface environment through aquifers.
Puge 7-2
SIPM Deiiiliitl: Mmunl, EP 93-1315, Rev 1.1. Niiv 1993, File nume = 7CHAP.DOC
7.2.5.
Select a suitable process location for the water treatment system (4)
Most water treatment equipment is located at the end of the process, often operating at or close to atmospheric pressure. However, whenever possible, consideration should be given to locating deoiling equipment further upstream in the process. Many types of deoiling equipment may be operated at elevated pressures (e.9. hydrocyclones, plate pack interceptors, flotation, filters etc.) This minimises the pressure drop between the water source and the water treatment equipment, thus minimising shear forces and maximising hydrocarbon droplet sizes. If possible, shear inducing devices such as control valves should be located downstream of water treatment facilities. Waste water streams are typically combined from a number of sources, however in many cases the flow from just one source may provide the bulk of the water. Consideration should be given to separate treatment at the source of the bulk waste water stream. An excellent example is a conventional three stage oil separation train. The bulk of the water is often separated in the first stage separator at a relatively high pressure, yet all this water is usually let down to a low pressure in order that the relatively small water streams from subsequent separators can report to a common low pressure water treatment system. A more effective installation may be to operate water treatment system immediately downstream of the first separator at an elevated pressure. The bulk of the water would then be effectively treated without being sheared through level control valves. The relatively low flows of water from other sources could be pumped to the water treatment system using low shear pumps or treated in separate facilities. Similarly, it may be found that the majority of contamination may come from just one source. Treating the contaminated stream separately may be more efficient than mixing the streams then having to remove the same contaminants from a larger stream. Consideration should also be given to the process conditions that will affect the separation mechanism. As discussed in Appendix F, the separation of two phases following Stokes Law will be sensitive to a number of variables which are affected by process conditions. In particular, the density differential and viscosity will be functions of the process temperature and the selection of the process location should consider the potential effect on the phase separation of the operating temperature.
7.2.6.
7.2.7.
SlPM Deiiilinz
Miiiiii~il, EP
As a result, it is common practice to split the deoiling process into a number of stages. Operating with stages in series allows good results to be achieved with lower unit efficiencies, for example two deoiling stages in series operating at a relaxed 80% efficiency will have the same overall performance as a single stage operating at a 96% efficiency.
Operating with two or more stages also allows the upstream stages to optimise the feed conditions for the downstream stages, removing surges in flow rates or concentrations. The actual number of stages required will be determined by the ratio between the concentration of hydrocarbons or contaminants in the feed stream, and the quality requirements imposed on the effluent stream. In most cases at least two treatment stages will be required. Water treatment equipment can be broadly divided into the four stages illustrated in Table 7.1
Table 7.1 Typical water treatment stages and associated equipment Primary Treatment Skim tanks API separators Plate pack interceptors Shell standard CPI plate pack Coarse coalescers Secondary Treatment Induced gas flotation Dissolvedgas flotation Static hydrocyclones Rotary hydrocyclones Centrifuges Fine coalescers Polishing Treatment Crushed nut shell filters Dual media filters Cartridge filters Pre-coat filtration Membranes Tertiary Treatment Gas stripping Steam stripping Biological treatment Activated carbon absorption Solvent extraction Primary treatment is usually designed for the removal of large hydrocarbon droplets, large solid-particlesand hydrocarbon slugs. The primary stage will often be designed to absorb flow surges to provide a stable feed to subsequent water treatment stages.
Secondary treatment encompasses the bulk of deoiling equipment used in E & P operations. Secondary treatment is usually sufficient to reduce the dispersed hydrocarbon content below typical offshore discharge levels of 40 mgh (provided the droplet size and other water characteristics are within the operating envelope of the equipment).
Polishing stages are used for the further removal of dispersed hydrocarbons to levels typically below 10 mgh. Various filters are the most common methods used for polishing stage treatment. Polishing stages are often required where water is to be re-injected,for disposal from inshore or onshore based installations, or where feed is to pass to a tertiary treatment stage. Tertiary treatment encompasses techniques required to produce an effluent stream of high quality. Typical requirementsare a total hydrocarbon content of less than 5 r n g ,with strict restrictions on other variables such as BOD, heavy metals etc. Tertiary treatment encompasses a range of processes, with stripping techniques and biological methods most commonly used.
7.2.8.
PLlfie 7-4
SlPM DroilirrX Mnrrrrol. El 93-131.5, Hcv 1.1, NIIV1993, Filr n(inic = 7CHAP.DOC
Hydrocyclones
4
I
Centrifuges
Filtration
I I
10
100
lo00
It is apparent from Figure 7.2 that a number of water treatment equipment designs can be used to separate a given droplet size distribution. Once the droplet size criteria has been satisfied the selection of the water treatment system is governed by factors such as; Size and weight (particularly offshore) Capital cost Operating cost Ease of operation Maintenance requirements Flexibility of operation Generation of secondary waste streams
As a guide, Table 7.2 presents some guidance for the selection of different water treatment equipment designs. However, it must be stressed that for effective equipment selection all the steps presented in Figure 7.1 , particularly water and droplet size characterisation, should be followed.
For further guidance on the selection of deoiling equipment, the user is referred to the equipment summary tables presented in section 8.1 and the detailed discussions covering each equipment design presented in chapters 8 and 9.
7.2.9.
7.2.1 0.
Puxe 7-5
A Shell standard plate pack design for onshore, atmospheric pressure applications. Good choice for drain waters, ballast waters etc.
Relatively inefficient. Typically selected on secondary considerations such as providing surge capacity or if conditions do not allow a plate pack design. For most applications superseded by the Shell CPI design. May be used upstream to enhance the performance of skim tanks.
Becoming preferred method of deoiling, especially offshore. Potential drawbacks are relatively high capital costs compared to flotation and less flexible performmce compared to rotary hydrocyclonesor centrifuges. Lower capex than alternativesand properly configured can give excellent performance. However, has higher weight and space, higher opex (chemical injection) and may require more operator attention.
Dissolvedgas flotation Same comments as for induced gas flotation. Rotary hydrocyclones Falls between hydrocyclonesand centrifuges on price and performance. Should be considered if more flexibility or better performance than static hydrocyclone is required, but at a lower cost than a centrifuge. Should be considered for low flow, difficult separations such as water from gadcondensate operations. Excellent separation performance for dispersed hydrocarbons and solids, but expensive. Often only choice for difficult separations. Should be considered for low flow, difficult separations such as water from gas/condensate operations. Can be used upstream to enhance the performance of secondary equipment.
Centrifuges
Fine coalescers
Polishing T r e a t m e n t
Crushed nut shell filters Recommendedfor the filtration of produced water with dispersed hydrocarbon concentrations up to the order of 150 mg/l. Dual media filters Can be used for produced water with a low dispersed hydrocarbonconcentration, preferably less than 50 m u . Used where solidhydrocarbon loading is very low, for example as guard filters downstream of media type filters. Good performanceif solids and oil content are low (e5 m g ) , however generally not recommendeddue to problems with handling and disposing of pre-coat. Show promise but require further development for most deoiling applications. Could be considered for low flows of relatively clean (non fouling) waste waters.
Puge 7-6
SIPM Deoilinji Munucrl, EP 93-1315. Rev 1.1, Nov 1993. File numc
= 7CHAP.DOC
Tertiary Treatment
Air stripping
Commonly used onshore, relatively cheap. However requires suitable path for disposal of contaminated stripping gas. Presence of oxygen may cause problems Typically uses nitrogen or lean hydrocarbongas. Eliminates oxygen related problems, but oflen more expensive than air stripping. Nitrogen stripping requires source of nitrogen. Lean hydrocarbongas stripping may need compression to recover hydrocarbon gases. More expensive than gas stripping, however has the advantage in that the waste gas stream is relatively easily treated by condensation. Commonly used onshore to treat water to a standard required for disposal into inland waters e.g. rivers, lakes. Mainly used for the removal of dissolved organic contaminants. Salinity and variability of productionwaters may impose limitations. May be used for removal of low levels of specific contaminants such as heavy metals and hydrocarbons. However, regeneration or disposal of spend carbon must be addressed. May be effective if suitable solvent is readily available and there is a suitable solvent disposal or treatment route. KSLA compact design under development.
Gas stripping
7 . 3 . 7 . 3 . 1 .
7 . 3 . 2 .
7 . 3 . 3 .
SIPM Droilinl: Mmual. EP 93-1315, Rev 1.1, Nov 1993, Filr tionie = 7CIIAP.DOC
Puge 7-7
7.3.5.
7.3.6.
Recycle streams
The effect of recycle streams on process integration should be carefully considered. Recycle streams may often be contaminated with solids, chemicals or bacteria and recycling these streams may result in accumulation in the process. In particular, sludges or tight emulsions which accumulate at hydrocarbon/water interfaces should not be recycled to the process without appropriate treatment to break down the inherent stability of the sludge or emulsion. Where possible, reject streams from any equipment should be disposed by injecting into the hydrocarbon export stream provided sufficient dilution exists to avoid exceeding export quality specifications. This avoids the use of recycle streams. Alternatively, recycle streams may be processed in dedicated sludge or emulsion treating facilities. Treatment requirements for reject streams should be considered as part of the overall water treatment system. For example, conventional dual media filtration systems require additional equipment for the treatment of dirty back wash water.
7.3.7.
7.3.8.
Treatment chemicals
A wide range of treatment chemicals are commonly used to assist the production process such as demulsifiers, deoilers, antifoams, corrosion inhibitors and hydrate inhibitors.
Whenever a process chemical is used, its potential impact on the entire process system should be
Pup? 7-8
SIPM Drrriliiig
Mtiiiri~~l, EP
7.4.
7.5.
7.6.
SlPM Droilinji Moiiirtrl. Et 93-1.715. Rrig 1.1. Nov 1993. Fill, iiiriiie = ?CllAf.DOC
P u p 7-9
1NT
Puge 7-10
SlPM Deoilinx Miriiuul, EP 93-1315. Rev 1.1, Nnv 1993, File nume = 7CHAP.DOC
INTRODUCTION
Scope of chapter
Chapter 8 presents discussions on a range of proven deoiling equipment for the removal of dispersed hydrocarbons from water. Where applicable each discussion includes information on equipment design principles, performance characteristics and sizing guidelines. For the removal of dissolved hydrocarbons from water the user is referred to Chapter 9, while Chapter 10 presents new and as yet unproven technologies which may be used for the removal of dissolved and/or dispersed hydrocarbons from water. When considering any design or operational deoiling problem it is strongly recommended that the user reviews the system design information presented in Chapter 7. Improvements in deoiling equipment design or operation can often be made by consideration of the deoiling system within the context of the overall process. This is particularly true with respect to the influence of upstream shear characteristics on the droplet size distribution of the dispersed hydrocarbons reaching the deoiling process. Effective integration of the water treatment system into the overall system design'will result in the most efficient and cost effective solution.
8.1.2.
SIPM Deoiling Mimid. EP 93-1315. Rrv 1.1. Nnv 1993. File n m i e = XOIINTR0.DOC
Puxe 8-I-I
Hydrocarbon removal efficiencies and outlet 111 concentrations 111 Coarse Upstream of other Coarse coalescer Higher hydrocarbon Dependanton inlet coalescers separation equipment. designs do not affect concentrationspromote droplet size. Refer to May be designed as droplets smaller than coalescence. No upper individualcases given e.g. combined coalescers 40 pm. limit on hydrocarbon in the summary serpentine concentration. tables in relevant paths. coarse and separators. section 01 Chapter 8. packlng Fine coalescers Typically cartridge type designs. Media bed COaleSCer8 Upstream of other separation equipment. May be designedas combined filters, coalescersand separators. Upstream of other Separation equipment. Usually designed as combined coalescers and separators. Cartridge designs can Higher hydrocatton coalesce droplets concentrations promote down to at least 10 coalescence. however pm. may result in greater louling.
Equipment
Location
Solids handling
chemicals
Use of
Advantages
Disadvantages
Some (but not all) coarse Not normally coalescers can be used. designed to handle solids wilhout blockage.
Examples include SP packs, structured packing etc. Should improve the separation pertormance of downstream equipment. Coarse design resists blockage by fouling and solids, but limits coalescingpower lor small droplets. Excellent coalescing ability for small droplets. Particularly useful for condensate/water applications where droplet sizes are small but water flow rate is relatively low.
Coarse COaleSCerS Will Only improve performanceof downstream coarse separation equipment such as senling tanks. No significant coalescing effect lor small hydrocarbon droplets.
Dependant on inlet Cartridge designs will droplet size. Refer to block with solids. thus individualcases given solids in the feed should in the summary be minimised. May tables in relevant require cheap guard filter section of Chapter 8. upstream. Similar to a media High hydrocarbon Typically in the order Excessive solids will filter can coalesce concentrationswill of 15 m y l in the block media bed more droplets down to the assist coalescence but outlet stream. rapidly. Usually cleaned may result in more rapid by backwashing. order of 2 10 5 pm. fouling. High hydrocarbon Not applicable. concentrationscan be tolerated as not actually separating hydrocarbons. Rates of chemical addition may need to be adjustedto suit. No restriction Dependant on inlet droplet size. Reler to individualcases given in the summary tables in relevant section of Chapter 8.
performance Fine cartndge bul COal may eSCerS be too have large good and expensive for large water flow rates. Cartridgeswill be fouled by some oils and by solids.
Coagulation Upstream of Droplets down to the Flocculation separation equipment. order of 2 to 5 pm Often used before can be coagulated. filtration or dissolved air flotation.
Designs often use oleophitic media or chemicals to make the media oteophilic. Dependson application Use coagulants to promote and chemistry of coagulation/flocculation. coalescence and Some solids may be poly-electrolytes bound into flocs and to promote removed. Others may Ilocculation. simply settle out. Solids will settle in tank Not normally or vessel, allowance can used. be made for accumulation and removal by jelling or manual cieaninq.
Gwd coalescence performance. Usually Media can be fouled by Some achieves coalescence and separation in a hydrocarbons. Equipment is relatively single vessel. Also removes solids. large and heavy.
Will increase the apparent droplet size. Requireschemicals. Downstream improving downstreamseparation. May be separation must be gentle to avoid destroyingflocs. able to flocculate solids to aid their removal by flotation or sedimentation.
150 pm
Provide surge capacity, remove slugs of Large weight and space requirements. hydrocatbans, Homogenisestreams from Short circuiting likely in larger tanks and vessels. Under typical design flow rates different sources, simple to operate. will only separate relatively large droplets.
SlPM DeiJilinXMunuul. EP Y3-1315. Rev 1.1. NIIV 1993. File numc = TABS-/.DOC
Minimum droplet size separated API separators Pnmary separation, usually open to atmosphere
50 pin
J pm
Hydrocarbon removal efficiencies and outlet 111 concentrations [l] No restriction Typically 50 to 100 m@. However very dependenton droplet size in feed No restriction. Typically 40 lo 100 performance will m@. However very depend on droplet size dependent on droplet dislribulion. size in feed. Inlet concentration Typically 80 l o 90% should typically be lower removal, 20 lo 30 m9/1 in outlet stream. than 400 mgA to achieve 40 m@ outlet However very spec. However, dependent on droplet performance will size in feed. depend on droplet size distnbution
Solids handling
Use of chemicats
Advantages
Disadvantages
Solids will settle on bollom. May be continuously removed by scraper bars. Solids should be \lot normally removed before entenng JSed the actual plate pack lo avoid blocking plates.
Large space requirements Allows oxygen ingress Superseded by CPI plate pack interceptor desgn Plates can block with solids or fouling Plate pack spacing should be higher where solids or fouling IS expected which reduces separation performance Performancedetenoratesat non design conditions Oil reject ports may block with light solid materials High solids concentration may result in erosion
Hydrocyclones
Can be used as pnmary water lrealment provided solids and hydrocarboi concentrations are acceptable May be used as coalescers if relect stream closed Can be used as pnmary water treatment
3tot5pm
Rotary hydrocyclones
to 10 pm
own lo 2 pm
Low solids concentration acceptable, exits with water phase. High solids concentration may result in erosion, especially for high pressure drop applications. Can use special liners to minimisf erosion. Inlet concentration Typicalty 85 lo 95%. Low solids concentration Uot normally should typically be lower Typically 15 to 25 acceptable. Not as JSed than 600 m@ to mg4. However very subject lo erosion as a achieve 40 m@loutlet dependent on droplet static hydrocyclone. spec. However, size in feed. However solids may performance will accumulate. reducing depend on droplet size separation performance. Idistribution. I ITypically should be ITypically 90 lo 98% lCan handle up to 5% Vot normally ised
Good pnmary separation device which can degas liquids, remove solids and slugs of hydrocarbons Compact gravity separation device StandardShell CPI design available which supersedes API desiqns Compact robust design especially for \lot normally )sed, however in onshore applications Can be designed for high pressure and installedupstream of ,ome cases control valves Modular design allows leoilers have capacity 10 be increasedas required New mproved the designs improve separationperformance ,eparation at lower pressure drops )erformance Compact, separation efficiency higher than static hydrocyclones designs and more constant over a range ot operating conditions Performancelies between hydrocycloneand centrifuge,however more compact and requires less power than centnfuges Excellent separation performance Can separate water, hydrocarbons and solids Performancestable over a wide range of operating conditions
High weight space and cost compared lo hydrocyclones especially for large water flows Added complexity of high power consumption Low capacity per individual unit (=lo0mVh) Examples where poor performance experienced Very dependent on water chemistry and steady operation Field trials recommended Chemical trials required to optimise performance
only be used at low pressure Relatively
3eoilers and Doiyelectrolytes ,hen used to work indicates otherwise mprove Ilotation Derformance
I
I
In many cases can achieve excellent performanceunder steady conditions Now available in pressure vessel configurations
. N m /Y9.3.
I1 I Inlet urid tirifler hydrocurbon :im'entrurions rind efficiencie.\ ure typiwl only.
In miist cues performunce ujill depend on dnipler size disrributiim. U.rer.s should refer t o the equipment simimuries U I the end ifniozt equipnient .sec.riin.s i n Chupfer X t o see the runge of results ribruined in d$ferent rriuls und operuting in.rtullutims.
Equipment
Location
Secondary treatment, 2 to 5 pm (using ,ecommendedused in Ilocculation) :onjunction with :oagutation and ,locculation Tertiary treatment 2 pm
Recommended hydrocarbon inlet concentrations [l] Typically should be less than 500 mgl to ensure a satisfactoryeffluent.
Hydrocarbon Solids handling Use of removal efficiencies chemicals and outlet concentrations [l] Typically 80 to 90% Variable effects, should Upstream removal, 10 to 40 be avoided unless test flocculants and work indicates otherwise. polyelectrolytes mgl in effluent. used. Solids removed. Should be less than 50 mg/l in feed to ensure adequate length 01 filtration cycle.
Advantages
Disadvantages
In many cases can achieve excellent performanceunder steady conditions. Flotationaction is gentle enough to be used with upstream llocculation.
Without upstreamCoagulationand flocculation induced gas IlOtatlOn is prefened. Relatively large and heavy equipment.
Crushed nut Tertiary treatment shell media filters and oleophilic media filters Cartridge filters Polishing treatment. 3fIen used as guard fitters lor water injeclion. Polishing treatment
Tertiary treatment
Equipment large and heavy. Media Can be louled by high hydrocarbon concentrations in feed or waxy or fouling hydrocarbons. Requiresadditionaltanks to store both clean and dim/ backwash I I I I I ]water. 12 pm Ilnlet oil content should IRemoval of 95% of ISolids removedby !Not typically ]High quality water effluent. usually suitablelEquipmentlarge and heavy. Tends 10 be slightly heavier than equivalent dual lorwater injection. More resistant lo be less than 150 mgl. particles greater than filtration. Solids removal used. HCI media system. Each filter has an Some experience to 200 2 pm. Typically < 5 not as effective as dual iniection used in hydrocarbon fouling than other media mgn. mgl in effluent. media filters. some locations filters, Can be backwashed with dirty associatedpump lor backwashing to prevent water. Do not need vessels lor clean and increasing maintenance requirements. formation 01 iron dirty backwash water. Lower volume of precipitates, back wash water produced. Only suitable lor polishing duties due lo High quality water eflluent, absolute Not normally Hydrocarboncontent Solids removedby Typically 2.0 pm, Can be absolute particle size ratings available. Compact cost of cartridge replacement. used. should be very low ( 4 rated down to 0.6pm. filtration. Solids level down to 0.6 pm equipment design. mgl) to avoid frequent Typically < 1 mg4 in shoukd be low to avoid cartridge replacement. effluent. frequent cartridge I replacement I I I IDown to 2 ptm IFilter pre-coat ]High quality water effluent Used in water IRequirescontinuousdosing of tiller aid llnlet oit content should IRemoval of 98% of )Solids removed by Facilities must be providedfor storage treatment plants for stream raising be lower than 15 mgl. particles greater lhan filtration. Solids should required. and preparation01 filter aid, and systems. 2 pm. Typically < 1 typically be less than 5 disposal of lilter aid cake after filtration. mgll in effluent. mqlt. As low as possible if Typically 10 mg/l in Solids will not pass Alcoa Petrolux Potentially very compact size. Good Not sufficientlydeveloped. Membrane Depends on membrane type. loulingis likely. effluent. through membrane. uses coagulant effluent quality. New improved membranes fouling reduces flux rates. Cleaning Typically down to at Should be minimisedto to improve being developed. systems need to be improved and
Inlet oil content should Removal of 98% of be lower than 30 mgl. particles greater lhan Some experience to 100 2 pm. Typically < 5 mgh. mg4 in eflluent.
Upstream High quality water effluent. typically coagulant and suitable lor water injection. llocculantsoRen used to improve performance.
SfPM Drrriling funuul. EP 93.13iS. Rev 1.1. Nnv 1993. File numr
= TAEX-/.DOC
11 I lnler und outler hydrtnurbrm concenrrutiims und efticiencies ure ryicul only. In most u s e s perjiirmunce will depend 1 1 1 1 droplet size drsiriburion. Users should reJer to the equipment sunimuries ut the end ofmo.sr equipment seciiimr in Chuprer 8 10 see the runge i,fresults obruined in digerenr rriuls und operufing insrulluriiins.
Hydrocarbon removal efficiency is a simple percentage efficiency relating the feed and product oil concentration. It does not consider the quantity of the product and reject streams, only the quality of the product compared to the feed.
Hydrocarbon removal efficiency (%): EOil = 1-
- x 100
Eq. 8.2.1
The process efficiency takes the process flow rates into consideration and will thus indicate a poor efficiency for a process which generates a large reject stream.
Ep=
( ~L~~~
1--
)x( 1-R)xlOO
Eq. 8.2.2
Where:
R
CF C , QF 0 , Q ,
= reject ratio =
=
[?)
The major deficiency of these definitions is that they do not consider the size distribution of the dispersed hydrocarbons in the feed stream. Thus, while a particular class of deoiling equipment may have 100% hydrocarbon removal efficiency for 50 pm droplets, it may have a 0% hydrocarbon removal efficiency for 5 pm droplets. Thus these efficiencies are only a measure of deoiling performance at a particular droplet size distribution. The expression for hydrocarbon removal efficiency highlights an obvious, though often overlooked principle of water deoiling. No deoiling equipment can guarantee an absolute effluent quality, only a relative reduction in hydrocarbon concentration. This leads to the following important guidelines for the design and operation of deoiling equipment.
No matter how efficient the deoiling equipment, in most cases high hydrocarbon concentrations in the feed will result in high hydrocarbon concentrations in the outlet. When trying to improve overall deoiling performance, it may be easier to lower the inlet hydrocarbon concentration (by improvements to upstream equipment) rather than striving for marginal improvements in the performance of the deoiling equipment alone.
Higher overall removal efficiencies may be obtained by operating deoiling equipment in series. For example, two deoiling stages in series operating at a relaxed 80% efficiency will have the same overall performance as a single stage operating at a 96% efficiency. These guidelines are discussed further in Chapter 7, Equipment Selection and System Integration.
wlie
= 802DEFIN.DOC
P u p 8-2-1
PURL? 8-2-2
SIPM Deoilinl: Mcrnucrl, EP 93-1315, Rev 1.1, Nov 1993. File nome = 802DEFlN.DOC
COALESCERS
General
The performance of most deoiling equipment for the removal of dispersed hydrocarbons is strongly influenced by the size of the hydrocarbon droplets in the feed stream with larger droplets being easier to separate. Coalescers are devices designed to promote the coalescence of small hydrocarbon droplets into larger droplets. Many coalescers do not actually separate hydrocarbons from water, however they aim to improve the separation performance of downstream equipment by increasing the hydrocarbon droplet size in the feed to these downstream units. There are a wide range of coalescing devices available from equipment suppliers. However, in general all coalescing devices are based on the principle of increasing the probability of contact between the dispersed hydrocarbon droplets. If the conditions are suitable, the droplets can then coalesce to create larger droplets. By definition, a coalescing device does not separate the hydrocarbon and water phases, merely alters the droplet size distribution. In practice, many coalescing devices are packaged as combined coalescers/separators.
8.3.2.
Definitions
The following equation may be used to define the coalescing performance of a coalescing device. It calculates the percentage change in the volume of hydrocarbon contained in droplets smaller than a nominated cut-off diameter. The cut-off diameter of interest is usually selected on the basis of the minimum droplet size required for the efficient operation of downstream separation equipment. For example, if a plate interceptor type separator was to be used downstream of a coalescer, a useful cut-off diameter would be in the order of 40 pm, as illustrated in equation 8.3.1.
% < 40,
Coalescing efficiency =
- % < 40,
% < 40,
Eq. 8.3.1
Where:
Yo < 40,
% < 40, = % of hydrocarbon volume in droplets less than 40pm in the product
8.3.3.
Performance variables
8.3.3.3.
Emulsion stabilisers/destabilisers
The coalescence process is the opposite of emulsification. Thus any factors that tend to stabilise emulsions will reduce the coalescence performance. This may include stabilising surfactant chemicals, fine solids and the other emulsion stabilisers discussed in Chapter 3.0. Conversely, processes which destabilise emulsions will improve the coalescing performance, such as deoiling chemicals that increase the interfacial tension between the phases. Emulsion destabilisers are also discussed in more detail in Chapter 3.0. The effect of surface active chemicals on the surfaces of coalescing elements must also be considered.
nii~~= i e UOXOAL
DOC
Pugc 8-3-1
8.3.4.
Installation/Configuration
Process location
The function of a coalescing device is to coalesce small dispersed hydrocarbon droplets into larger droplets. Thus coalescing devices should preferably be located immediately upstream of the separation equipment that is to take advantage of the larger droplets created by the device. Potential sources of shear forces between the coalescing device and the separation equipment should be eliminated or minimised. In most cases, the coalescing device will be packaged as an combined coalescer-separator, such as vessels or tanks with coalescing devices on the inlet stream plate pack separators.
8.3.4.1.
8.3.5.
Coalescer designs
8.3.5.1. General
There are a wide range of coalescer designs available from vendors. The broad classes of coalescer design are introduced in the following discussions, while additional detail on a range of specific coalescing equipment is included in Appendix G. Also included in Appendix G are figures illustrating the coalescing performance of five of the designs which were tested at the Orkney Water Test Centre in 1991. Table 8.3.1 summarises the performance of coalescers from a range of trials and installations. For more detailed information the user is referred to the full OWTC report (EP 92-0942) and the reports EP 891365 (Ref.2.14.2.c) and EP 89-1366 (Ref.2.14.2.c) which investigate the performance of a range of coalescer elements.
8.3.5.2.
Coarse coalescers
Coarse coalescers are robust designs used to promote the coalescence of relatively large hydrocarbon droplets. They do not have a significant coalescing effect on droplets smaller than 40 pm. Coarse coalescers have the advantage of being relatively cheap and may often be designed to be tolerant of solids in the feed stream. They are suitable for relatively simple coalescing duties upstream of coarse separation equipment such as skimming tanks and separators. Examples of coarse coalescers includes the Knitmesh DC coalescing mesh, MPE SP Pack, Monosep Spiralsep and various types of structured packings. Plate pack interceptors can also be considered a form of coarse coalescer.
8.3.5.3.
Fine coalescers
Fine coalescers have a relatively dense coalescing media which can give good coalescing performance for small droplets. They are typically packaged into cartridge type designs similar to cartridge filters. The flow is normally from the inside of the cartridge to the outside, ensuring the fluid velocity through the coalescing media decreases as it passes through the cartridge. The coalescing media is normally oleophilic, allowing the hydrocarbon droplets to "wet" the media, encouraging coalescence. The outer later of the cartridge may be hydrophilic to encourage the release of the coalesced droplets. The potential drawbacks of cartridge type coalescers is that solids in the feed stream will tend to block the element and due to a relatively low capacity per coalescer element number of elements required for large water flow rates may be prohibitive. Examples of fine coalescers include cartridge type designs available from Knitmesh, Pall, Peco, Plenty Metro1 etc.
8.3.5.4.
Puge 8-3-2
SIPM Drnilin# Mirnuol, EP 93-1315. Rrv 1.1, Nov 1993. File numc = XO3COAL.DOC
8.3.5.5.Hydrocyclone coalescers
Hydrocyclones may be operated in a coalescing mode by blocking off the hydrocarbon reject port, forcing the hydrocarbon core in the centre of the hydrocyclone to exit with the water stream. The centrifugal forces force the dispersed hydrocarbon droplets into close contact in the core of the hydrocyclone, promoting coalescence. Trials at the OWTC indicated relatively good coalescing performance, especially when a recycle stream was used or two hydrocyclones were operated in series. KSLA also noted this during hydrocyclone trials.
8.3.5.6.Hydraulic coalescence
In some cases, hydraulic coalescence could be considered an alternative to the mechanical coalescers discussed in the preceding discussions. Hydraulic coalescence can be achieved by contacting the water stream containing dispersed hydrocarbons with a suitable coalescing hydrocarbon stream, such as a product crude oil stream or even a dedicated recirculating hydrocarbon stream. A suitable hydrocarbon stream should be selected on the basis of low solubility in water, a high density difference from the water stream and good separation characteristics. The presence of the additional hydrocarbons droplets of the coalescing hydrocarbon steam will increase the probability of collisions between dispersed hydrocarbon droplets and encourage the coalescence of the original dispersed hydrocarbons droplets into the coalescing hydrocarbon phase. By avoiding excessive shearing forces, the bulk water and hydrocarbon phases should be relatively simple to separate. The water phase with residual hydrocarbons can then be passed to normal downstream deoiling equipment. After the hydraulic coalescence the overall hydrocarbon concentration remaining in the water should be lower and the dispersed hydrocarbon droplets should have a larger mean diameter. In addition to coalescing dispersed hydrocarbons, a suitable solvent may also be able to remove dissolved hydrocarbons. This is the basis of the extraction process discussed in section 9.7.
SIPM Droilinfi
Miittiid,
PuKe 8-3-3
Location
Equipment
SP Pack insidf skim tank. Coarse coalescer Knitmesh Dusec, line coalescer
Field trial or installed Inlet Deta equipment hydrocarbon date of equipment installatlon concentration in brackets) (mgn) istalled equipment (1990). 1990 184 to 433 quipment tested with and Typically 280 rithout chemicals (Reverse mulsion breaker - REB) quipment testing centre 1991 Tested at 50,100.400 and
Solids handling
Use of chemicals
Comments
Relerence
OWTC
With REB 53% Not applicable for coalescer lor coalescer coalescing abilih, used 600 without separato Nithout separator when solids present. Though1 to be due to solids stabilisation of emulsion. lSee comments I 1991 Not applicable Tested at Not aDDlicable ILower I Not normallv 50,100,400 and for coalescer coalescingabilih, used lor c&escer without separatoi Nithout separator when solids BM) present. Though1 to be due to solids stabilisation of emulsion. See comments Not applicable 1991 Tested at Not applicable Difficult to Not normally lor coalescer discern effect of used 50,100,400 and lor coalescer without separato Nithout separator solids due to low 800 coalescing
Better Perfonance of skim tank without SP pack was performance very poar (8% oil removal). Installing SP pack using reverse improved removal to 32%. using deoiling emulsion breaker chemicals further improved removalto 53%
2.14.2.b
performance, especiallyfor small droplets. During trials with solids coalescingperformancecontinued Summary in Appendix D to decline, suggestingpossible solids accumulationin coalescer. Performance not considered as effectivein lresh water.
ICoalescinaabililv lound to imDrove with increasina IEP 92-0942 hydrocarbon droplet size and concentration. Suitable as a coarse coalescer. During trials with Appendix D solids coalescing performancecontinuedto decline, suggestingpossible solids accumulation coalescer.
93-1315, Rev
I. Nov
Coalescingability found to improve with increasing EP 92-0942 hydrocatboon droplet size and concentration. Performance poor for low concentrationsor small Summary in droplet sizes. Suitable only as a coarse coalescer. Appendix D
Location
Equipment
OWTC
OWTC
lvortoil hydrocyclone in coalescing mode, line coalescer MPE SP Pack, Equipment testing centre coarse coalescer
I I
Field trial or installed Inlet Date equipment hydrocarbon (data of equipment Installetlor concentration (mgtl) In brackets) Equipment testing centre 1991 Tested at 50,100,400 and
1991
Solids handling
Comments
Reference
800
Not applicable Not applicable Not tested lor coalescer lor coalescer without separator without separator
used
Australia, North Knitmesh Rankin and Goodwyn. Dusec, Peco Laboratow trials element. PleOh/ element. Fine coalescers Australia, Goodwyn platform, Laboratory trials Cobham AFG, Knitmesh Dusec, Warner Lewis, Peco. Fine coalescers
Laboratorycomparison of coalescing performance. NOTE Tests for coalescing water in condensate. NOT oil In water. Laboratorycomparison 01 coalescing performance. NOTE: Tests for coalescing water In condensate, NOT oil in water.
Tested at Not applicable Not applicable Lower lor coalescer coalescing ability 50,100,400 and lor coalescer without separator without separator when solids 800 present. Thought to be due to solids stabilisation01 emulsion. 1988 Tested with loo0 Not applicable Not applicable Not tested ppm condensate for coalescer for coalescer in water reed without separator without separator stream
Found to give relativeiy good coalescing performance. An optimum throughput must be found which promotes coalescence but does not incur droplet shear. Coalescence improved when the recycle to the cyclone was increased. Coalescing ability found to improve with increasing hydrocarbon droplet size and concentration.Effect 01 solids considered to be due to emulsion stabilisation by solids. Suitable as a coarse coalescer.
7C
1989 Tested with loo0 Not aDDliCable Not aoolicable Not tested .. ppm condensate lor coalescer lor coalescer without separator without separator in water
Re12 14.2.d Range 01 experiments investigaingcoalescing01 dispersedwater in condensate. For this application Knitmesh gave better performance than Peco elements. Plenty element gave paor performance. Corrosion inhibitor appeared to alter coalescer media properties01 all elements and reduce performance. Corrosion Five different coalescina elements were tested lor Re1.2.14.2.c inhibitor lound to the removal 01water droplets from condensate hinder the The Knitmesh Dusec and Alan Cobham C6-1450coalescing M were found to be the best performers Corrosion lability inhibitor reduced the performance01 all Corrosion inhibitor lound to significantly hinder the coalescing ability.
Puge 8-3-6
SlPM Deoilinl: Munual, EP 93-1315. Rev 1.1. Nov 1993, F i k nome = 803COAL.DOC
8.4.1.2.
Flocculation After the coagulation stage the water passes to the flocculation stage. Flocculation is the process by which the initial microflocs formed by coagulation are agglomerated into larger flocs. The flocculation procedure is assisted by residence time and gentle agitation. Polyelectrolytes (known as flocculants) are usually added to improve the flocculation process. These are long chain, water soluble polymers with excess electrical charges along their length which help to gather the microflocs into larger flocs. The type of flocculant to be used is dependent on the characteristics of the water and suspended droplets and solids and is established through laboratory tests. Flocculants are typically used in dosages of 0.5 to 10 mg/l. Where minimal weight or space are important, serpentine path flocculators can be used to achieve flocculation in a relatively compact design. A jar test procedure for testing the effectiveness of coagulants and flocculants is presented in the reference "Standard practice for coagulation-flocculation jar test of water", ASTM D 2035-80, Ref Ref.l.05.3.b.
8.4.2.
Floc separation
The coagulation/flocculation process on its own does not remove dispersed hydrocarbons or suspended solids from water, merely concentrates these impurities into larger, more easily separated flocs. A number of separation processes may be used downstream or in combination with the flocculation process.
8.4.2.1.
Filtration Coagulants and flocculants are often used to aid filtration. As well as aiding the formation of flocs the flocculant will improve the adhesion of the flocs to the filter media. Typical dosage rates are 0.5 mg/l of coagulant (e.9. ferric chloride) and 0.5 mg/l of flocculant. For filtration duties, coagulants and flocculants are often simply injected directly into the process piping upstream of the filters. In-line mixers can be used to ensure quick dispersion of the chemicals. Due to potential interaction of the chemicals, coagulant and flocculant should not be injected at the same point. Coagulant should be injected as far upstream as possible to give the coagulant sufficient time to form microflocs without interference. Sources of shear forces such as control valves should be avoided, especially after the addition of the flocculant. Flocculation performance may be improved by use of a serpentine flocculator upstream of the filters.
SIPM Droiling Mrmunl. EP 93-1315, Rev 1.1. Nov 1993, F i k nnmr = XO4FLOC.DOC
Puge 8-4-1
8.4.2.3. Sedimentation
Flocculation/sedimentation is widely used for the removal of suspended solids. The agglomerated flocs of particles will settle at a higher rate than the individual solid particles.
The sedimentation process can be applied to the removal of dispersed hydrocarbons if there are sufficient solid particles present to give the flocs of hydrocarbons and solids a negative buoyancy. Alternatively weighting agents such as active silica can be added to improve the settling characteristics of the flocs.
8.4.3.
Operation considerations
P U ~ 8-4-2 C
SlPM Deoilinp Mimuiil. EP 93-13IS. Rev 1.1, Nov 1993, File ncimr = XO4FLOC.DOC
8.5.2.
Performance variables
The performance of a skimmer is generally governed by the variables present in Stokes law. Stokes law is discussed in detail in Appendix F.
As with all separation equipment governed by Stokes law, the hydrocarbon droplet size is the most important variable affecting the separation performance. Droplet sizes should be maximised by avoiding shearing and promoting coalescence wherever possible.
Skimmers are usually sized for separation of hydrocarbon droplets of size 150 pm or larger.
8.5.3.
Installation/Configuration
As skimmers are generally designed to remove relatively large hydrocarbon droplets, they should preferably be located upstream of level control valves to minimise shearing of hydrocarbon droplets. However this will often conflict with the common requirement for degassing and a low design pressure.
8.5.4.
8.5.4.1.
Design guidelines
8.5.4.2.
SIPM Deoilruji M ~ I I I I IEP ~I~ 93-1315, , Rev I 1. Nov 1993. File i i w i e = XO5SKIMT DOC
Puge 8 - 5 1
8.5.4.4.Coalescing devices
As with all separation equipment based on the application of Stokes law, the separation performance will improve if the size of the dispersed hydrocarbon droplets can be increased. If large skim tanks are to be used, consideration should be given to the installation of a simple coalescing device on the inlet stream to maximise the droplet size. The coalescing device should be a relatively simple and robust design such as a plate pack, MPE SP Pack, Natco Performax or similar. These devices are particularly suitable for fitting to skim tanks to improve throughput or separation performance. Due to the relatively large size of most skim tanks these coalescing devices can oflen be installed inside the tank itself.
8.5.5.
Control configuration
P U ~8-5-2 C
Oil layer
Oil skimmer
L
Elevation
Water
Plan
Water inlet
Figure 8.5.2 Schematic diagram of a skim tank designed to API separator type guidelines
SlPM DeoilinfiM i m u d . EP 93-1315. Rev 1.1. Nov 1993. File minie = X0SSKIMT.DOC
Puxe 8-5-3
Page 8 - 3 4
SIPM Deoilinji M(iiruci1.EP 93-1315. Rev 1.1. Nov 1993. File minw = 8OSSKIMT.DOC
8.6.2.
Design guidelines
Oil risers
n7wmP
8.6.3.
Caisson internals
lnternals can be fitted to improve the hydrocarbon separation performance of a disposal caisson. However, with the increased complexity of upstream deoiling equipment (e.g. hydrocyclones followed by degassing tanks capable of capturing hydrocarbon slugs), the use of caissons incorporating internals and oil recovery systems has declined.
8.6.3.2.SP Piles
MPE market a caisson design fitted with a number of SP Pack coalescing packs to improve the separation performance.
II(IIIIY =
XO6SKIMP.I)OC
Puxe 8-6-1
8.6.4.
Operational considerations
8.6.4.1.
Wave action
The design of the caisson will only operate satisfactorily during periods of relatively low wave action. As wave height grows, the caisson will be subject to a piston pumping action and will be unlikely to achieve any significant separation.
Puge 8-6-2
SIPM DroilinK Umuctl. EP 93-1315, Rev 1.1. Now 1993, File nome = XO6SKIUP.DOC
8.7.2.
Performance variables
The separation characteristics of an API separator are governed by Stokes law. The theory of Stokes law is discussed in Appendix F. In general the API separator is designed for the removal of hydrocarbon droplets larger than 150 pm.
Installation/Configuration
Process location The API separator is a primary separation device. It may be used as the first stage in a two or three stage water treatment plant, or for the treatment of large water flows with easily separated hydrocarbons such as drains water or ballast waters. The size and weight of the API separator design prevents its use offshore.
8.7.3.2.
Oil skimming
A number of skimming devices are available for the removal of collected hydrocarbons from the surface of the water including rotary drums, slotted pipe skimmers, horseshoe floating skimmers and self adjusting floating skimmers. These are discussed in detail in the referenced guidelines.
A modification to the rotating drum type skimmer is the use of a oleophilic film on the surface of the drum. This makes the drum more efficient at hydrocarbon skimming while minimising the quantity of water carried over with the recovered hydrocarbons. The system can be fitted to existing API separators. If required, more details can be obtained from SlPM EPD/421 (Ref. 2.03.1 .d)
8.7.4.
8.7.4.1.
Design guidelines
API separators
The design of an API separator is covered in detail in the following references. Manual on Disposal Of Refinery Wastes, Liquid Wastes, 1st ed, 1969, American Petroleum Institute (API), Chapter 5 and 6 Drainage and primary treatment systems, DEP 34.14.20.31-Gen, May 1986 Amended by Circular No.29/86, Custodian MFSH. New revision expected early 1994 (Ref..2.04.1 .e). These references give the following guidelines for the sizing of the separation channel for an API separator. Maximum horizontal velocity in the separation channel is 0.015 m/sec or 15 times the hydrocarbon droplet rising velocity (whichever is smaller). The dimensions of the separator channel should fall within the following ranges. Depth (metres): 0.9 c d < 2.4 Width (metres): 1.8 c w < 6.0 d Ratio: 0.3 < - c
W
0.5
Unless provision is made for continuous sludge removal, an allowance of 0.3 meters should be made for the accumulation of sediment on the bottom of the separator channel 8.7.4.2. Shell Parallel Plate Interceptors The design of the Shell Parallel Plate Interceptor is discussed in detail in the following references.
0
Manual on the Shell parallel plate interceptor, No report number, MF document (Ref.2.03.1 .a) Standard drawings, SIPM/SICM, S I4.001 and drawings referenced thereon.
P U ~ 8-7-2 C
SIPM Droiliiih. Mmuol, EP 93-1315. Rev 1.1. Nov 1993, File nume = XO7API.DOC
Sludge collection hoppers I Trash rack Diffusion device Sludge discharge with lead plug
Flights
'\
ELEVATION
Figure 8.7.1 API separator with two separation channels and no skimming facilities on the inlet section
EP 660715 MQ9
SlPM Deoilinji Mmuol. EP 93-1315, Rev 1.1. Nov 1993, File twne = XO7APIDOC
Puge 8-7-3
Puxe 8-7-4
SIPM Deniling Mmrcnl, EP 93-1315, Rev 1.1. Nov 1993, File nome = 807API.DOC
8.8.1.
8.8.2.
8.8.2.1.
Performance variables
Hydrocarbon droplet size As a gravity based separation device, the performance of a plate interceptor is broadly governed by the variables present in Stokes law (Appendix F). The dominant variable in Stokes law is the hydrocarbon droplet size and any increase in the mean hydrocarbon droplet size in the feed to a plate interceptor will improve the hydrocarbon removal efficiency. Where possible, the plate interceptor should be located in a process location with the largest possible droplet size. A typical plate interceptor will remove droplets down to the order of 60 pm.
8.8.2.2.
Plate spacing and inclination The spacing between plates is normally in the order of 20 to 40 mm. The closer 20mm spacing will remove smaller hydrocarbon droplets. However if blockage of the plates due to solids, wax deposition, scaling or fouling is possible the wider 40mm spacing is usually specified. The plates are normally aligned at 45" to 60" from the horizontal. The steeper angles are used in the presence of solids to assist their removal from the plate pack.
8.8.2.3.
Stable flow regime The separation performance of the plate pack is dependent on maintaining a stable laminar flow regime through the plates. Factors which could upset the flow regime and should be avoided include; Flow surges. There should be no rapid changes in the flow rate entering the plate pack. Obstructions. These may take the form of plate pack supports, jetting nozzles, drains etc. These should be positioned and designed to minimise any turbulence they might induce. Solids and fouling. The accumulation of solids or fouling upstream of the plate pack or on the surfaces of the plates themselves will disturb the flow pattern and upset the flow regime. The performance of the plate pack will deteriorate over time if such accumulations are not removed.
8.8.2.4.
Reynolds number One of the main criteria governing the design and performance of plate packs is the Reynolds number. Limits are imposed on the Reynolds number to ensure that the flow regime in the plate pack remains laminar.
Iicune
= X0XPIATE.DOC
Puxe 8-8-1
up flow
An up flow design is illustrated in Figure 8.8.2. The up flow design has the advantage that the hydrocarbon droplets and hydrocarbon film on the underside of the plates are moving in the same direction as the flow of the water. Fingers are often used on the top of the plates to allow the hydrocarbons to accumulate and coalesce before leaving the plate. Separation of the hydrocarbons and water is after the plate pack. The disadvantage of the up flow design is that the upward fluid flow will hinder the settling of solids through the pack, making the plate pack more susceptible to blockage when suspended solids are present in the feed stream. Cross flow A cross flow design is illustrated in Figure 8.8.3. The water flows horizontally across the plates and does not preferentially favour the separation of hydrocarbons or solids. The cross flow design has the advantage in that it can be efficiently packaged into different configurations. As it does not need excess space above or below the plates for the entry and exit of the water flow it can often utilise more of the available vessel volume than alternative designs. This is a particular advantage in pressure vessels, where a cross flow design can fill more of the available cross-sectional area with plates and thus minimise the overall size of the vessel.
Oily wa in
'
H7Y)mmP
H75m8/10P
Hydrocarbons
Y er
HIWlIP
Puxe 8-8-2
SIPM Deoilinh. M(muu1, EP 93-1315. Rev 1.1. Niiv 1993, File nome
= X0XPIATE.DOC
If a high solids loading is expected the up flow configuration or a cross flow configuration with the flow along the corrugations should not be used due to the risk of plate blockage.
8.8.2.6.
Corrugated plates
In a plate pack consisting of flat plates, the hydrocarbon droplets accumulating on the bottom surface of the plates will be relatively evenly distributed across the surface of the plates. This even distribution will not assist coalescence of the hydrocarbon droplets. Figure 8.8.4 illustrates the behaviour of hydrocarbons and solids in a down flow corrugated plate pack with the flow along the corrugations. The same arrangement could be used for an upflow configuration. A cross flow configuration would typically have the flow entering from the side, flowing across, not along, the corrugations.
The rising hydrocarbon droplets will be concentrated in the concave surfaces under the corrugated plates. This accumulation in the corrugations will assist in the coalescence of the droplets and improves the separation performance of the plate pack. Solids will tend to concentrate in the troughs on the upper surfaces of the corrugated plates. Unfortunately, no information has been found which can actually demonstrate whether corrugated plates have better coalescing properties than flat plates. On this basis both flat plates and corrugated plates must be considered equally acceptable. The only constraints on the use of corrugated plates are; If solids are present the corrugations must be aligned to allow solids to move out of the plate pack without being trapped by the corrugations.
HIS02(Yl??
If the flow direction is across the corrugations the allowable Reynolds number (400) is lower than if the flow is along the line of the corrugations (800).
8 . 8 . 3 .
8.8.3.1.
Installation/Configuration
Process location
Plate interceptors can be built into pressure vessels and thus can be installed at any point in the water treatment process. They are often installed as a first stage in a water treatment system, designed for removal of the bulk of the dispersed hydrocarbon before a second treatment stage. However where the process allows the plate pack should be used as far upstream as possible, upstream of level control valves and if conditions permit, even in primary separators. Figures 8.8.5 to 8.8.8 illustrate a range of possible configurations. Plate packs are often successfully used for single stage treatment of streams with large oil droplets such as deck and drains water and ballast water treatment. As with any deoiling equipment where the separation is governed by Stokes law, every effort should be taken to minimise the shearing forces and to encourage coalescence upstream of the plate interceptor.
liiitiie
= XOXPIATE.DOC
P u p 8-8-3
Number of platepacks 4
16
8 8
10.1
L 6 5 . 8
Comments Single pack Single bank, 4 in row Single bank, 8 in row Double bank, 4 in each row Double bank, 8 in each row
5 . 6 10.1
4.6 4 . 6 8 . 3 8 . 3
3.5 3.5 3 . 5 3 . 5
120
30
8.8.4.
Design guidelines
8.8.4.1. Sizing
The sizing of plate packs for a given separation duty is discussed in Appendix H. The key criteria to be satisfied are; The Reynolds number through the plate pack should be equal or less than 800 for any flat plate configuration, or for corrugated plates where the flow is along the corrugations. The minimum hydrocarbon droplet size that can typically be separated in a conventional plate pack is in the order of 60 microns. Higher Reynolds numbers and more turbulence (up to 1500) can be tolerated if the hydrocarbon droplets are large or if a lower separation performance is acceptable. The Reynolds number through the plate pack should be equal or less than 400 for a corrugated plate configuration with the flow across the corrugations. The separation performance of the plate pack will be governed by the relative dimensions of the plate pack. These dimensions determine whether a rising hydrocarbon droplet will intercept a plate before leaving the plate pack.
Drainage and primary treatment systems, DEP 34.14.20.31-Gen, May 1986 Amended by Circular No.29/86, Custodian MFSH. New revision expected early 1994 (Ref.2.04.1 .e) Deoiling industrial waste water. Design and operation of the CPI (Corrugated plate interceptor)
P q e 8-8-4
SlPM Deoiliiifi M~tnuol, EP 93-1315, Rev 1.1. Nov 1993, File numr = X0XPLATE.DOC
8.8.5.
Operational considerations
8.8.5.1.
Solids handling
If solids are expected in the feed stream the design should allow for their removal. Rapidly settling solids can be allowed to settle in a stilling zone before entering the plate pack. Finer solids and sludge will settle at the bottom of the plated section. Appropriate nozzles and jetting systems should be provided for removal of accumulated solids.
8.8.5.2.
Plate pack removal In many applications the plate pack may eventually be blocked due to fouling or accumulation of solids. Provision should be made for suitable access and lifting equipment to allow the removal of the plate pack for cleaning or replacement as required.
I I
---i--?
Treated water
. ,
u4
Sludge
iiiiiiie
= X0XPLATE.DOC
Puge 8-8-5
Flow distributor
Treated water
Figure 8.8.6 Down flow plate pack Possible pressure vessel configuration (Skimovex)
HIY)26157P
Hydrocarbons discharge
Treated water
Sand outlet
Sludge outlet
Figure 8.8.7 Cross flow plate pack Pressure vessel configuration (Rossmark-Pielkenrood)
Paxe 8-R-6
SlPM Droiling Monica/, EP 93-1315, Rev 1.1. Nov 1993, File nnme = X0XPlATE.DOC
OUTLET WEIR
OIL SKIMMER
INLET BAFFLE
00
n o
4 OFF
CPI PACKS
EP 660714 M I S
Location
Equipment
Inlet Field trial or Installed Date hydrocarbon equipment (date of equipment Installation concentration (mg/l) In brackets) 150 Short field trial with small 5 mJ/h 1981 test unit. Not given Installed equipment (1982) 1993
8010100
1993
5010 150
Non Corrosive Installed equipment (1978) UK, North Sea, Cormorant A platform Metal Products UK tilted plate separators UK, North Sea, Dunlin Non Corrosive Installed equipment. Includes platlorm. including Metal Products treatment of water from the Osprey development UK tilted plate Osprey development. Osprey separators results in ifalics(Os).
2106
2106
(Os)300 to 400
25 to 30
24 to 29
(OS) 200 to 300
. .
Notknown
I
vessel
Notused
I
I Not used
INot used
Units perform relatively satisfactorily.System to be 1993 deoiling upgraded during the Forcardos terminal upgrades. questionnaire I I Performgnce is claimed to deteriorate with 11993 deoilino I
lincreasinqfeed concentration.
11993 deoilinn
lquestionnaire
Iquestionnai;
section
H7rn1.1P
By maintaining a suitable pressure ratio between the clean water outlet stream and the reject oil outlet stream, the geometry of the hydrocyclone will result in the thin hydrocarbon core flowing in a reverse direction, exiting from the top of the swirl chamber. The clean water exits from the tail section of the hydrocyclone.
8.9.2.
Definitions
The following definitions are commonly used for hydrocyclones. Feed: Underflow: Reject stream or Overflow: Reject ratio (R): The oily water feed stream entering the hydrocyclone The clean water stream exiting from the tail of the hydrocyclone The concentrated hydrocarbon stream exiting from the head of the hydrocyclone though the reject port. The ratio of the reject and feed stream volumetric flow rates:
8.9.3.
Performance variables
8.9.3.1.
Introduction
The flow patterns and forces acting within a hydrocyclone are very complex and unlike traditional gravity based separation equipment cannot be simply described in terms of Stokes law. Appendix I presents a discussion of the some of the methods which can be used to model hydrocyclone separation
8.9.3.2.
Hydrocarbon droplet size Stokes law (Appendix F) illustrates that diameter is the dominant variable affecting the buoyancy of a hydrocarbon droplet. Although Stokes law cannot be directly applied to a hydrocyclone, the droplet size will have a similar effect on the buoyancy forces which cause the hydrocarbon droplet to migrate to the centre of the hydrocyclone. Thus, as the size of a hydrocarbon droplet increases, the rising velocity of the droplet increases and the droplet has a higher probability of migrating to the reject oil stream. Similarly, as the droplet size decreases, there will be a reduced probability that the droplet will migrate to the reject oil stream and an increased probability of the hydrocarbon droplet exiting with the water stream. This behaviour is illustrated in Figure 8.9.2 where it can be seen that a droplet size of 6 microns has only a 56% probability of being separated from the water stream.
110
100 80
90
70 60
50
40
30 20
10
10
15
35
40
45
As a result, it is important to maximise the droplet size reaching the hydrocyclone by avoiding shearing and promoting coalescence wherever possible. Hydrocyclones should be located close to the source of the oily water, preferably upstream of control valves. For pumped hydrocyclone installations, the feed pumps should be a low shear design. The cut-off droplet diameter for a hydrocyclone is dependant on a number of variables such as water viscosity, density differences etc. However, as a guide, it can be assumed that the current generation of hydrocyclones will have difficulty separating droplets smaller than 10-15 prn when operating at design conditions. Separation of droplet sizes in the order of 6 to 7 pm can be achieved using the latest designs of
Pujie 8-9-2
SlPM Drorlrnl: Mitriinrl, EP 93-131.5. Krv I 1. Nov 1993. File nome = XG9CYCLO DOC
8.9.3.3.
Flow rate
The physical geometry of the hydrocyclone is designed to generate the optimum swirl characteristics at a particular design flow rate, maximising the centrifugal separation acceleration while minimising shearing of the dispersed phase into smaller droplets. At low flow rates, separation is reduced due to lower centrifugal forces. This behaviour is illustrated in Figure 8.9.3 where it can be seen that as the flow rate is reduced, the value of d7, rises, indicating reduced separation performance. In general, to achieve satisfactory separation it is recommended that hydrocyclones are not operated below 40% of their design capacity.
20.0
17.5
15.0
E, ; ;12.5
u
IC.
10.0
7.5
5.0
10
20
30
40
50
60
70
80
90
100
110
120
Figure 8.9.3 Variation in hydrocyclone performance with flow rate (% of design capacity)
At some point above the design flow capacity the performance of the hydrocyclone will deteriorate. This deterioration can be due to a number of factors. At higher flow rates more shearing may be experienced in the hydrocyclone, reducing droplet size and separation performance. As flow rates increase, the pressure drop across the hydrocyclone will increase until eventually the available feed pressure is not sufficient to drive the reject stream out of the hydrocyclone. Even before this point is reached, the increased pressure drop may lead to gas breakout in the hydrocarbon core, upsetting the performance of the hydrocyclone.
8.9.3.4.
Inlet hydrocarbon concentration Hydrocyclones can tolerate large surges in oil concentrations. Normal hydrocarbon removal efficiencies have been observed with hydrocarbon concentrations in the order of 12,000 mg/l hydrocarbons. However, it must be recognised that the hydrocarbon removal efficiency is simply a ratio between the inlet and outlet hydrocarbon concentrations. Thus as the inlet concentration rises, the outlet concentration will also rise. Figure 8.9.4. illustrates a number of effects of higher feed concentrations on hydrocyclone performance. Firstly, as shown by the points marked by squares, as the hydrocarbon content of the feed increases the separation efficiency of the hydrocyclone also increases. The reason for this improvement is apparent from the figures in the small table included within the figure. It can be seen that as the hydrocarbon concentration increases, the average droplet size also increases. This increase in droplet size is due to the higher chance of droplet collisions and coalescence at the higher hydrocarbon concentrations. The hydrocyclone can more readily remove the larger droplets, hence the separation performance of the hydrocyclone improves. Secondly, the bars on Figure 8.9.4highlight the relationship between separation efficiency and outlet concentrations. It can be seen that even though the separation performance of the hydrocyclone improves with the increasing feed concentration, at a feed concentration of 500 mg/l the outlet concentration has exceeded the desired concentration of 40 mg/l. At a feed of 2200 mg/l, the outlet
8
Y _.
90
80 3 70 --
-* - /
I I I
FI
;/*
/CJ---
----- 100 -- 80
r-
-.- 60
! .
50 -40 --
ccncmtrabom for constant shear rate 13pm 0 50 mgl 52pm (B 900 mgl M P m 8 203 mgl 66pm (D 1500 mgh
.E
c
L
i5
30 -- I I 20 -- I
_ _ _ _
-- 60
_ _ _- - 4 0
8 ..c m
-- 20 a
0
- - - - Efficiency required to
achieve 40mg4
Figure 8.9.4 Variation in hydrocyclone performance with feed concentration at constant shear
Secondly, it can be seen that the efficiency of the hydrocyclone tends to increase with increasing hydrocarbon feed content. This is to be expected as the larger droplet sizes with the higher hydrocarbon concentrations will be easier for the hydrocyclone to separate. Eventually the removal efficiency gains become marginal with increasing feed hydrocarbon content. This behaviour is thought to represent a balance between the coalescing forces of the higher hydrocarbon content and the shearing forces being exerted on the large hydrocarbon droplets inside the hydrocyclone.
Puge 8-9-4
SlPM Deiii/iriK Mirnutrl, EP 93-1315. Rev 1.1, NIIV 1993, File nome = XO9CYCLO.DOC
Table 8.9.1 Recommended settings for reject ratio Hydrocarbon content in feed Up to 1% hydrocarbon Up to 2% hydrocarbon Recommended setting
4%
10%
20.0 17.5
E, 10
r .
7.5 .
I
100
50
150
Density difference (kg/rrP)
I
200 250
It should be remembered that characteristics of the hydrocarbons other than density difference will also
SlPM Duoilinl: Mioirrirl, EP 93-1315, RKV1.1. Niiv 1993, File r i i i r i w = XO9CYCLO.DOC
Puge 8-9-5
E,
Y
-0
9.0 7.0
5.0
0.20
0.60
.oo
1.40
2.20
Temperature may have additional effects on the hydrocarbon/water emulsion, such as altering surface tension or altering emulsion stability. These effects may influence the overall hydrocyclone performance. 8.9.3.8. Pressure drop Definitions Under normal operation there are two distinct pressure drops across a hydrocyclone.
Where:
Pin = Feed stream pressure Pout= Water outlet stream pressure Prej = Hydrocarbon reject stream outlet
The pressure drop to the reject stream (ALP2) is the most significant as it is the greater of the two and will ultimately determine the capacity of the hydrocyclone. At an early stage in the development of hydrocyclones it was found that C, the ratio between AP2and AP, has a linear relationship with the reject ratio, as illustrated in Equation 8.9.1.
c = Pi" - Pour
Where:
C R
= constant
Pin - Prej
) [2)
=
is proportional to R
Eq. 8.9.1
= reject ratio
Puae 8-9-6
The slope of the curves in Figure 8.9.8 are characteristic for each hydrocyclone installation, but are mainly a function of the geometry of the hydrocyclone. As the pressures in and out of the hydrocyclone are easily measured, this relationship may be used as the basis for measurement and control of the reject ratio of the hydrocyclone. 8.9.3.9.
iiiime
= XOYCYCLO.DOC
Puxe 8-9-7
InstallationKonfiguration
8.9.4.3. Packaging
Depending on the available pressure drop the capacity of a single hydrocyclone is in the order of 4 to 20 mVh. To achieve the capacity required to process larger flow rates, individual cyclones are assembled into packages with multiple hydrocyclones in parallel. The most common packaging bundles a number of hydrocyclones into a pressure vessel with common header space for inlet and outlet streams. This modular packaging of most hydrocyclone installations has a number of distinct advantages. The capacity of the water treatment system can be upgraded by adding additional hydrocyclone packages. Thus future water treatment capacity can be phased in as required. Turn-down of the system can be accomplished by adjusting the number of hydrocyclones modules on-line. This ensures on-line hydrocyclones are operating at optimum efficiencies.
It may be possible to upgrade or replace the hydrocyclone liners whilst retaining the external pressure vessel housing.
The possibility of water escaping from the system is reduced as the number of flanges and connections is minimised and as the hydrocyclone liner is enclosed by a pressure vessel, erosion of the liner will not result in external leakage. Modular hydrocyclone packages may be dedicated to individual water sources, thus allowing level control valves to be located downstream of the hydrocyclones.
Coalescing operation
Hydrocyclones can be configured to act as coalescence devices. For this mode of operation the reject stream is blanked off and the nominal capacity of the hydrocyclone reduced. As for a normal separation service, the hydrocarbon droplets migrate to the centre of the cyclone where they have a higher chance of coalescence. Both water and hydrocarbon streams exit from the underflow of the hydrocyclone. For more detailed information the user is referred to Section 8.3 which discusses coalescing devices.
8.9.5.
8.9.5.1.
Control configuration
Flow control
A suitable method of controlling a hydrocyclone would be to maintain a suitable ratio between the flow rates of the reject stream and the feed stream. However in practice it is difficult to obtain accurate measurements of the reject stream flow rate due to gas breakout and the difficulty in measuring two phase flow. Because of this, hydrocyclones are controlled on a basis of pressure differentials.
8.9.5.2.
Control mode Hydrocyclones have a very low residence time and will quickly establish the flow regime required to achieve separation. On this basis a hydrocyclone configuration with a single feed source will operate satisfactorily with an intermittent feed stream (such as from an on-off level control scheme). Operation with multiple on-off control sources should be avoided as the hydrocyclone installation would have to be designed for the total combined flow from all sources, but in practice, the installation would often be operating under turn-down conditions.
8.9.5.3.
4"I'pii
I
DP
Hydrocarbons
W?!%L,SP
F k ; ;
Ralm
- - - _ - - - - - - - r - - - - -
*PI
Setpoint
;AP,
+*I-:
I
c+--
Hydrocarbons
Water
H7W17P
Puge 8-9-9
,
Hydrocarbons Water
The control of the overflow and reject ratio can be Figure 8.9.11 performed using the pressure differential ratio Control Multiple feed hydrocyclone control scheme discussed in the previous section. For clarity the differential pressure transmitters have not been illustrated in Figure 8.9.4.
mwMP
Although in some cases the use of a common hydrocyclone is required, the use of individual hydrocyclone packages with control valves located downstream of the hydrocyclones is generally preferred. This maximises the droplet size in the feed to the hydrocyclone and will thus improve the hydrocarbon removal efficiency.
; " I * ,
m F J
Fc
If there is spare capacity available in the upstream vessel, the recycle stream may be recycled back to the inlet of the water source vessel. This has the advantage of allowing additional residence time for the small recycled hydrocarbon droplets to coalesce.
Positive disolacement pumps
Hydrocarbons
Water
Positive displacement pumps are normally progressive cavity pumps (e.g. Moyno) which have low shear characteristics. The pump speed should be set to pump at a rate slightly higher than the maximum water rate expected from the water source. This will ensure that the system always operates with some recycle and can absorb any higher than normal water rates without regularly adjusting the speed of the pump. A 10% recycle is typical. The combination of the positive displacement pump and the recycling water stream will maintain a set flow through the hydrocyclone, even under turn-down conditions. This ensures that the flow through the hydrocyclone is always sufficient to ensure a high separation efficiency. Centrifuaal pumos Provided they are designed for low shear operation, centrifugal pumps may also be used for hydrocyclone feed pumps. Vortoil suggest the following criteria for centrifugal pumps to minimise shear forces in the pump; Slow speed e.g. a four pole motor speed (ca. 1800 rpm 6 3 60Hz) High pump efficiency, preferably > 70% Large discharge nozzle (velocity preferably less than 5.5 m/s) High specific speed, preferably N , > 700 Closed impeller design (to minimise slippage)
Poge 8-9-10
SlPM Deoiliny: Mmuol, EP 93-1315. Rev 1.1. Nov 1993, File name = XG9CYCLO.DOC
8.9.6.
Operational considerations
8.9.6.1.
A backwashing system should be specified on the reject oil stream. The backwashing system uses a stream of water or gas to reverse the flow in the reject stream and remove any material blocking the exit port. The underflow from another hydrocyclone may be used for backwashing.
The reject stream should be blocked in downstream of the backflushing point to ensure the full flow of the backwashing is directed into through the reject port of the hydrocyclone and that any foreign material is carried out though the underflow of the hydrocyclone. Due to the short residence time in the hydrocyclone backflushing is only required for a short period e.g. 15 seconds.
8.9.6.3.
Operating experience
Hydrocyclones are considered a well established technology with numerous installations throughout the world. Table 8.9.2 summarises the operating performance of hydrocyclones in a range of Shell installations and trials.
SlPM DmilinK Mimacil. EP 93-1315. Rev 1.1. Nov 1993, File nciinc = Xo9CYCLO.DOC
Puxe R-9-ll
lo00
100
10
1
1 10
100
Pressure drop (bar) Figure 8.9.13 Variation in hydrocyclone capacity with available pressure drop Based on Vortoil K liner packaged modules (Jan 1993)
16.0
14.0 * 0
?
I
12.0
10.0
v)
a t ,
0.0
100
200
--
300
400
600
700 dp 15 bar
800
900
1000
dp5bar
-dplObar
- -x- -
Figure 8.9.14 Operating weight of hydrocyclone package (Low pressure drop applications) (See assumptions after Figure 8.9.17)
Page 8-9-12
SIPM Deoilinx Monutrl, EP 93-1315 Rev 1.1. Nov 1993. File nume = XWCYCL0.DOC
25.0
a
C ( I ) C
v)
20.0
.-
B 15.0 E m
c
.z 10.0
5.0
0.0
200
400
dp 20 bar
600
Capacity (mVh)
800
lo00
1200
1400
dp 25 bar
-X-
dp 30 bar
Figure 8.9.16 Operating weight of hydrocyclone package (High pressure drop applications) (See assumptions after Figure 8.9.17)
9.0
E 7.0
a
Y
8.0
a m ,
6.0
25 . 0
.- 2.0
L
. E3.0
u l
1.0
0.0
100
200
300
400
700
dp 15 bar
800
900
lo00
--* dp5bar
-dplObar
-XI
Figure 8.9.16 Footprint area of hydrocyclone package (Low pressure drop applications) (See assumptions after Figure 8.9.17)
SlPM Deoihnl: Mmwnl. EP 93-1312, Rev 1.1, Nnv 1993. Fde nome = XO9CYCLO DOC
Page 8-9-13
10.0 9.0
.&
v
7.0
4.0
1.0
0.0
200
- 400
600
800
1000
1200
1400
dp 20 bar
OX-
dp 30 bar
Figure 8.9.17 Footprint area of hydrocyclone package (High pressure drop applications)
AssumDtions for hvdrocvclone weiahts and footmint areas in Fiaures 8.9.14 to 8.9.17 1. 2. 3. Equipment sizes are based on Vortoil K liner packages Weights and sizes are for skid mounted packages inclusive of typical piping, valves, structural steel etc. Each skid contains 2 standard Vortoil K liner vessels with the maximum number of liners per vessel. Each vessel is sized for 50% of the required flow, thus a single skid represents a 2 x 50% package for the given flow rate.
Puge 8-9-14
SIPM Droiling M ~ n u t r l EP . 93-1315, Rrv 1.1, Nriv 1993, File name = 809CYCLO.DOC
Field trial or Installed Date Inlet Outlet Hydrocarbon Solids handling Use of equipment hydrocarbon concentration chemicals removal (date of equipment Installation efficiency concantratlon (mg/l) In brackets) (rngn) New Zealand. Maui A Vortoil K liners Field tests 1992 14 to 20,000+ 2 to 42 mgil 70 lo 99% Not known None used platform mg/l Typically 19 mg4
Oman. Onshore Marmul, Rima and Lekhwair oil fields
Location
Equipment
Comments
Reference
Field trials. Marmul (M) trials in normal typeface. rn underli n 4 and Lekhwair (L) trials are in italic.
AwaQEm(L) 8 lo 13
BlMW.44
RI A v e a rQ e Z -B i
(L)Average 44%
berage 48% Not known
Inlet concentrationvaned over wide range, outlet concentrationsg o d . Operates with a very high inlet oressure 1120 to 150 bar) with a oressure dra ]in the order of b0 bar. IChemicals found Ilnvestioations included measurement of drODlet to have a small size distributions.Cyclone efficiency was benefit. but not consideredto be poor due to very small droplet optimised. sizes in feed stream. Performance from the cyclone was relatively poor. Ignoring spurious results gives a typical efficiency of 65%. The high efficiencycyclone gave a higher efficiencyin the order of 70 to 75% and more consistent performance. The degassing vessel tended to lower the effluent oil level by a further 10% Not used KSLA investigation into droplet size distributionsat inlet and outlet of hydrocyclones. Determinedcut off diameler to be in the order of 10 to 15 pm. Not used Performance considered to be very good, especially when inlet hydrocarbon concentrations are very high. Not used, Upstreamuse of corrosion inhibitors results in a however see much higher concentration reponing lo the comments hydrocyclones, presumably due to a smaller regarding use of droplet size. However efficiency of cyclone was the CI same with or without CI. The K liner is more etficient than the 35 mm design. Flocculation agent recommended. Demulsifiers and corrosion inhibit. resulted in lower performance. Not used Various chemicals tried, none etfectivein trials
S.2.j
.5.2.f
52.e
UK, North Sea. North Vortoil(4 in 1 Detailed trials on an existing Cormorant platform design) installation, including KSLA droplet size analysis. Norway, Nonh Sea, Vortoil Installed equipment Murchison platform Norway,Troll west gas province Vortoil Trials conducted during production tests. Compared 35 mm cyclone and K liner. Also contrasted the performancewith and without corrosion inhibitor (CI). K liner results in italics (K). Equipment trials conducted during production tests Without CI 28
~
M to 95%
5 8 to 100% rypically 76%
35 mm 90% Yliner-94%
Without CI - 268
(K)W#b CI - 40 (K)Wffhouf Cl -
3 7 to 95%
Not known
Droplet size from oil separator measured as 65% .5.2.c smaller than 10 pm. Hydrocyclone performance alone was not good enough. However, it is proposedthat Chitosan be used to flocculate the oi droplets to improve the hydrocycloneperformance. Generallygood performance. Some sand blockageswhen upstream desanding cyclones are 993 deoiling uestionnaire
Typically
Typically 16mgl
3 0 %
SIPM Deoiling Munuul. EP 93-1315. Rrv I . I . Nov 1993. File numt = TAB8-9.1
)C
Location
Equipment
Vortoil
Field trial or Installed Date Inlet Outiet Hydrocarbon Solids handling Use of hydrocarbon concentration removal chemicals equipment (date of equipment Installation concentretion (mgrl) efficiency in brackets) (mgh) Not known Not used Commissioningtrials of installed 1993 Typically 40 mgl Typically 9 mgn Not given equipment (1992)
8 to 10 mgl 1993 Not known Est. Bo - 5OOrngl
Comments
Reference
UK, North Sea, North Vortoil(4 in 1 Installed equipment (1987 to Cormorant platform design) 1989) UK, North Sea, Vortoil Fulmar Alpha platform Norway, Draugen Merpro platform Montassa Hydropak OWTC BWN Vortoil Installed equipment (1992) Installed equipment (1993) Equipment testing centre
Est. 90%
Not used
Nolgiven
Not used
Results are from limited commissioningtests. Water production rates are currently too low for hydrocyclone operation. Normal performancegood. Some problems experienced with blockage of reject ports due to upstream HzS scavenger/demulsifier chemical trials. Recently installed (1992). Performance good. Platform to be commissioned October 1993
1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire t 993 deoiling questionnaire
-----
____.
_____
_____
...__
Scale inhibitor, demulsifier had no effect. Corrosion inhibitor reduced efficiency
Ranged from 15 Ranged from 50 Tested with 200 to 437 mgn to 82% mgn of 300pm Average 77% sand. No effect on performance.
OWTC
1990 Tested at 200, 8 20pm droplets 8 20pm droplets Not tested 400 and 6M) m@ c 40 rngl Efficiency 92%
8 W m droplets B 10pm droplets 40 to 120 m@ Elliciency 80%
1992 Tested from 50 Results from 15 Efficiency ranged Not tested 110 2200 mg4 110 180 mgl. lfrom wer 90% I for 30pm Vortoil and Krebs droplets down to gave best 70% for lOpm performance droplets 1993 Tested from 55 Results from 7 to Efficiency ranged Not tesled to968mgl 65mgll from 79 to 95%
SIPM Drrriling Munuol. EP 93-1315. Rev 1.1. Nov 1993. Fite nume = TABX-9.1
EP 90-2641 First series of OWTC trials comparing performance of a static hydrocyclone, rotary hydrocyclone and flotation unit: Variables tested includedflow rate, reject ratio, hydrocarbon concentration, droplet size, effect of chemicals, gas injection, water temperature and salinity. hydrocarbon density and effect of solids. EP 90-3599 Corrosion Second set of OWTC trials comparing inhibitor performance of a static hydrocyclone. rotary appeared to aid hydrocyclone and centriluge for separation of droplet condensate. Variables tested included flow rate. coalescence and hydrocarbon concentration, temperature. salinity. improved droplet size and effect of corrosion inhibitor. performance Not tested Third trial at O W C compared lour "New EP 92-1900 I Igeneration"hydrocyclones. Variables tested I included oil type, concentration. droplet size. water temperature and salinity, flow rate and reject ratio. Empiricalmodels were developed to allow the performance of the hydrocyclones to be predicted. EP 93-1492 Fourth trial at OWTC comparing new G and K Not tested liners against older F liner designs. Found no significant difference for large oil droplet sizes and concentrations, however K liner does perform significantlybetter for small droplet sizes and at low pressure drops.
8.10.2.
Definitions
The following definitions are commonly used for rotary as well as static hydrocyclones. Feed: Underflow: Reject stream: Reject ratio (R): The oily water feed stream entering the hydrocyclone
The clean water stream exiting from the tail of the hydrocyclone The concentrated hydrocarbon stream exiting the cyclone though the reject needle. The ratio of the reject and feed stream volumetric flow rates;
8.10.3.
Performance variables
The flow patterns and forces acting within a rotary hydrocyclone are complex and unlike traditional gravity based separation equipment cannot be simply described in terms of Stokes law. However, in general terms, the variables present in Stokes law will have an strong influence on the separation performance of the hydrocyclone and these variables are examined in the following discussions.
A number of graphs are presented illustrating the influence of some of the more important variables on separation performance. Where possible these results have been contrasted against the performance of
SlPM Driiilinx
Miiiiuiil.
EP 93-1.ZlS. Rrv 1. I .
Niiu
Puxe 8-10-1
10
20
30
40
50
60
70
80
90
100
W6117W
Rotary hydrocyclone
Given the significance of droplet size on the separation performance it is important to maximise the droplet size reaching the hydrocyclone by avoiding shearing and promoting coalescence wherever possible. Hydrocyclones should be located as close as possible to the source of the oily water, preferably upstream of control valves. For pumped hydrocyclone installations, the feed pumps should be a low shear design.
Puge 8-10-2
20
10
..x..
0
50
I*
8.10.3.3. Rotation speed
Figure 8.10.3 Hydrocarbon removal efficiency versus flow rate and rotation speed
--
200
250
W511703P
The speed of rotation of the rotary cyclone can be adjusted by controlling the speed of the driving motor. Figure 8.10.3 illustrates the effect of rotation speed changes on the separation efficiency of the hydrocyclone. It can be seen that as the speed of rotation increases, the separation efficiency increases due to the greater centrifugal forces being experienced within the cyclone. The rotation speed will also impact on the pressure drop and flow capacity of the cyclone. The higher the rotational speed, the higher the pressure drop across the cyclone, hence the lower the capacity. 8.10.3.4. Inlet hydrocarbon concentration
As with the static hydrocyclone, the rotary hydrocyclone will maintain a high efficiency in the presence of high inlet hydrocarbon concentrations. However, it must be recognised that the hydrocarbon removal efficiency is simply a ratio between the inlet and outlet hydrocarbon concentrations. Thus as the inlet concentration rises, the outlet concentration will also rise.
8.1 0.3.5. Pressure drop The geometry of the rotary hydrocyclone does not present the same type of flow restriction as a static hydrocyclone. The controlling aspect of the pressure drop across the rotary cyclone is not the geometry of the cyclone or the flow rate through the cyclone, but the losses induced by the rotation forces imposed on the liquid. Thus, although the pressure drop across the rotary hydrocyclone will increase with flow rate, this increase is not as dramatic as that for the static hydrocyclone. This behaviour is illustrated in Figures 8.10.4. and 8.10.5, showing the pressure drops to the product and reject streams respectively.
As expected, it can be seen that the pressure drop across the rotary hydrocyclone is more dependent on the rotation speed of the cyclone than on the flow rate through the cyclone. In contrast, above the design
SIPM Deoilinji Monuol, EP 93-1315. Rev 1.1, Nov 1993, File iiwne = XIODYNAM.DOC
Puge 8-10-3
As with the static hydrocyclone, it can also be seen that the pressure drop to the rotary hydrocyclone reject hydrocarbon stream is always higher than the pressure drop to the effluent water stream.
Figure 8.10.4 Pressure drop from the feed stream to the product stream for static and rotary hydrocyclones
....*....Static hydrocyclone
H76117IDIP
16
14
.... . ..... .
,,
. . .,
..
.. . . ..... .. ...
.. .
.. . .. . .
..
:y
12
10
. 0
6
4
2
0
50
200
250
mii7mw
L F
Figure 8.10.5 Pressure drop from the feed stream to the reiect stream for static and rotary hydrocyclones
P q e 8-10-4
SIPM Droilinji Monuol. EP 93-1315, Rev 1.1, NIJV1993, File name = XIODYNAM.DOC
8.10.4.
Installation/Configuration
8.10.4.1. Process location For systems to be operated from process pressure, the rotary hydrocyclone should preferably be located as close as possible to the source of the waste water, preferably upstream of level control valves to minimise shearing of hydrocarbon droplets. With multiple sources of water (e.9. independent separator trains), dedicated hydrocyclone systems for each source should be given preference to a single hydrocyclone package with individual level control valves located upstream of the hydrocyclones. The process location must consider the mechanical design limits of the cyclone. The design pressure is 20 barg with a maximum operating temperature of 110C. For pumped hydrocyclone systems low shear feed pumps must be specified. These are commonly progressive cavity style pumps or specially designed low shear centrifugal pumps. 8.1 0.4.2. Downstream degassing vessels If the feed stream to a hydrocyclone installation is from an elevated pressure, a downstream degassing vessel will normally be required to remove dissolved gases from the deoiled water stream before discharge. Careful design of the degassing vessel can utilise the generated gas bubbles to create a flotation effect in the vessel which can assist in the removal of the finely dispersed hydrocarbon droplets remaining in the water stream. Thus the degassing vessel should be designed to allow oil skimming from the surface. At the time of writing, one hydrocyclone vendor has applied to patent the use of a skimming vessel downstream of a hydrocyclone package however the validity of this patent application is under investigation. Experience indicates that a carefully designed degassing vessel can achieve further reductions in the effluent hydrocarbon concentration in the order of 10-15%. This reduction is sometimes supported by upstream polyelectrolyte addition. The degassing vessel is normally designed with a nominal residence time of 2 minutes to allow for degassing and some residence time to allow oil droplets to rise to the surface.. 8.10.4.3. Pressure drop - Definitions Under normal operation there are two distinct pressure drops across a hydrocyclone.
Where:
Pi, = Feed stream pressure Pout = Water outlet stream pressure Prej = Hydrocarbon reject stream outlet
The pressure drop to the reject stream (APJ is the most significant as it is the greater of the two and will ultimately determine the capacity of the hydrocyclone.
SIPM Deoiling Miiiiiid EP 93-1315, Rrv 1.1. Nov 1993. File
iiiiiiie
= XIODYNAM.DOC
PuRe 8-10-5
As previously discussed, the capacity of an individual rotary hydrocyclone is governed by the available pressure drop and the rotation speed of the cyclone.
Tables 8.10.1 and 8.10.2 give approximate sizes and weights for rotary hydrocyclone separation systems. These sizes have been taken from vendor brochures and should be treated as indicative only.
Table 8.10.1 Size and weight of single rotary hydrocyclones
2.5
3.4
4.6
6 . 1
10
Serck Baker Dynaclean brochure. Based on a 20vm droplet size, 150 Ib pressure class.
Table 8.10.2 Size and weight of typical hydrocyclone packages, each containing six horizontally mounted cyclones.
Floor area (m2) Height (m) Operating weight (tonnes) Power requirement (kW)
Source:
27.2
Serck Baker Dynaclean brochure. It is assumed that no standby cyclone included, therefore capacity will be reduced during maintenance.
8.10.5.
Design guidelines
There are no particular design guidelines for a rotary hydrocyclone. In general the vendor is responsible for the selection and design of a rotary hydrocyclone system to suit a given process.
PURC 8-10-6
SlPM Deoiling Monunl, EP 93-1315. Rev 1.1, Niiv 1993. File nome = 8IODYNAM.DOC
8.10.6.
Control configuration
a
FC
-----
Water
Hydrocarbons
HIYI2mIP
8.10.7.
Operational considerations
SIPM Deoilinji Moiwnl. EP 9.7-13lS. Rev 1. I * No\' 199.7. File iioiiir = XIOOYNAM.OOC
PURC 8-10-7
Location
Outlet concentration
(msn)
removal efficiency
Use of chemicals Scale inhibitor, demulsitier had no effect. accumulate until Corrosion inhibitor reduced a steady state reached. efficiency
Comments
Reference
EP 90-2641 First series of OWFC trials comparing performance of a static hydrocyclone, rotary hydrocyclone and flotation unit. Variables tested included flow rate. reject ratio, hydrocarbon concentration,droplet size, effect of chemicals, gas injection, water temperature and salinity, hydrocarbon density and effectof solids.
OWTC
Dynaclean rotary
Efficiency 92%
B 10pm droplets Efficiency 85%
B 1Opm40 to
120mgl
SlPM Droiling Munuul. EP 93-1315. Rev 1.1, Nov 1993. Fi/r num = TABX-IL
Performance of rotary hydrocyclone considered good with bener and more stable performance over a wider operating range than the static hydrocyclone. Against Second set of OWTC trials comparing EP 90-3599 sxpectalions use performance of a static hydrocyclone, rotary of corrosion hydrocyclone and centrifugefor separation of inhibitor condensate from water. Variables tested included appeared to aid flow rate, hydrocarbon concentration. temperature, droplet salinity, droplet size and effect of corrosion :oalescence and inhibitor. improved performance Performanceof rotary hydrocyclone considered good, fallingbetween static hydrocyclone and centrifuge.
I s
Feed
Hlm6/44P
An external motor rotates the bowl and disks at high speed, exerting a centrifugal force on the rotating liquid. From Stokes Law (Appendix F), the terminal velocity of a hydrocarbon droplet being separated by density difference is proportional to the gravitational force exerted on the droplet. In a centrifuge the gravitational force is replaced by a centrifugal force which is in the order of 5000 times higher, dramatically increasing the buoyant forces on a dispersed hydrocarbon droplet. The position of the hydrocarbonlwater interface within the centrifuge is a function of the fluid viscosities, densities, throughput and back pressures. The approximate position of the interface is fixed by selecting the correct size of gravity disc when installing the centrifuge. The gravity disk is effectively a restriction orifice controlling the dense phase (water) outlet rate. Once the gravity disc is in place, the interface position can be fine tuned by varying the backpressure on either of the liquid outlet streams Solid particles collect at the periphery of the bowl. Depending on the centrifuge design and solids loading the accumulated solids can be automatically discharged or periodically removed by manual cleaning. Figure 8.1 1.1 shows the Alfa-Lava1 Leo design which discharges solids by briefly lowering the bottom half of the centrifuge bowl. This allows solids and some water to be discharged through ports in the bowl wall, to be collected in an external bowl.
8.1 1.2.
Performance variables
iirriiir
= XIICENTR.DOC
Puxe 8-11-1
As the flow rate of water increases, the backpressure on the water phase will increase. This will tend to shift the interface towards the centre of the centrifuge. Eventually, water will start breaking through into the hydrocarbon outlet stream.
Under turn-down conditions the centrifuge will maintain high separation efficiencies due to the increased residence time.
8.1 1.3.
InstallationKonfiguration
8.11.3.3. Strainers
As with any rotating mechanical equipment, accidental introduction of any foreign material into the centrifuge may result in significant damage. Coarse strainers (300pm) should always be installed immediately upstream of the centrifuges to protect the centrifuge from foreign materials.
Capacity
(m3W
13 40 100 200
L
2.0 2.0 2.0 4.1
H
2.2 3.0 2.8 3.3
Configuration
1x 1x 1x 2x
SlPM Deoilinl: M~inutil. EP 93-1315. Rrv ].I# Niiv 1993, File ncimr = XIICEhTR.DOC
Page 8-11-3
P --
- - -;
Hydrocarbons
HIYIWVlOP
Automatic solids removal is controlled by a timer mechanism with the discharge interval set according to the rate of solids entering with the feed stream.
8.1 1.5.
Operational considerations
8.1 1.5.1. Maintenance As rotating equipment centrifuges require regular inspections and maintenance procedures. As a guide, an Alfa-Lava1 centrifuge typically requires an 8 hour shut-down every 3 months for a mechanical inspection. A major service (24 hours) is required once per year.
Puge 8-11-4
SIPM Deoilirtc: M(tnuct1, EP 93-1315, Rev 1.1. Nriv 1993, File riame = XIICENTR.DOC
Ana Laval
Ife5tr.
Alfa Lava1
Performance of centrifuge was good and 2.8.2.a considered independent of droplet size and significantly better than the parallel performance of static hydrocyclone. Field trial of centrifuge for I989 110 to 1017 mgl 14 to 61 mgl Average of 95% Handled solids Chemicals used Performanceof centriluge was good, both for Ref.2.8.2.f deoiling effluent water and for without difficulty for very high inlet deoiling water and breaking emulsions. Deoiling dewateringemulsions berage 548 Concentrations performance was significantlybetter than the Average 29 mgtl existing Wemco ftotatronsystem. 1991 :I)370 lo 427 (I)160 to 210 (I) 38 to 57% 4 to 8% by Chemicals used Centrifuge considered to work significantly better 2.8.2.c dirty feed streams. Trials volume to act as than other alternatives. The use of flocculants conductedon individualstreams LlQB-kW m n t o a% llocculants made a significant difference to the perfooance. .lw=ks% i o & without chemicals (I). The level of solids is very high and i f these solids 'Me) 3 8 3 to 840 (MC) 137 to 244 (MC) 63 to 69% are coated in oil this may be contributing and mixed streams !significantly to the oil content carried out in the 1 with chemicals (MC, itatics) Long term temporary installation I993 ?Oto6000mgl 12to200mgl 60% 20 to Boo mgl Flocculant used Centrifuge consideredto work relatively well. High 1993 deoiling installed Dec 1992 rypically 150 Typically 40 to upstream soliddsludge content in feed can choke centrifuge, questionnaire decanter to be installed upstream to remove solidslsludge. Sludge may be impactingon water quality. I993 500 to 2o00 mg4 20-30 mgl Not given Not known Not known Preliminary feedback suggests excellent Not yet with very small oil droplets. performance for a very difficult water. Unfortunately referenced Water could not be cleaned by large flow rate will require many units.
Data
Inlet Outlet Hydrocarbon Solids handling Use of hydrocarbon concentration removal chemicals concentration (men) efficiency (men) I992 200 to lo00 mgl 5 to 25 mgl Not given Not known No chemicals used
Comments
Reference
I"
OFPX 413
I990 rested at 200, 0 20pm droplets Constant Not tested 1 0 0 and 600 mgl 40 mgl eliiciency of higher than 92%, B 1Opm droplets independent of 40 to 120 mgl droplet size
Second set of OWTC trials comparing pedormance of a static hydrocyclone.rotary hydrocyclone and centrifugefor separation of condensate. Variables tested included flow rate, hydrocarbon concentration, temperature, salinity, droplet size and effect of corrosion inhibitor. Performance of centrifuge considered goad. achieving high hydrocarbon removal efficiencies even for small droplets. Dropletssize remainingin water stream was in the order of 7pm lor static cyclone, 511mfor dynamic cvclone and <2um for
EP 90-3599
I I SlPM Derrrlrng Munuuf. EP 93-131s. Rev I 1, Nov 1993, File numt = TAEX-11
oc
Puge 8-11-6
SIPM Deoilinl: M~tnuctl. EP 93-1315, Rev 1.1, Nov 1993, File nume = XIICEhTR.DOC
8.12.1.
Introduction
Gas flotation is a process by which dispersed hydrocarbon droplets are removed from water by attachment to rising gas bubbles. The oily froth which forms on the surface of the water is removed by skimming or overflowing to a collection trough. Gas flotation units are generally installed as a secondary stage in a water treatment system. Inert gases, air or hydrocarbon gas are normally used for induced gas flotation. In many cases the use of air is not practical due to the need to exclude oxygen from the process (the presence of oxygen leads to concerns with corrosion, biological growth and explosion hazard aspects). Chemical additives are often used to improve the performance of the flotation process. Gas flotation units are categorised by the method used to generate the bubbles, either Induced Gas Flotation (IGF) (mechanical and hydraulic) or Dissolved Gas Flotation (DGF). Induced gas flotation is the more common in E & P operations and is discussed in this section. Dissolved gas flotation is discussed in section 8.13. Mechanicallv induced aas flotation Figure 8.12.1 illustrates the design of a single mechanically induced gas flotation cell. Rotation of the impeller draws gas down the stand-pipe where it comes into contact with the oily water. The action of the impeller forces the water and gas through the disperser which results in the formation of small gas bubbles. The bubbles rise to the surface of the water, collecting hydrocarbon droplets and forming an oily froth on the surface of the water. The froth flows over a weir into an collecting launder, often assisted by mechanically driven paddles. The clean water underflows though a port or under a baffle near the bottom of the cell.
Shaft
Figure 8.12.1 Schematic diagram of a Wemco mechanically induced gas flotation cell
Hvdraulicallv induced aas flotation The operation of a hydraulically induced gas flotation cell is very similar to the mechanically induced gas flotation cell. However, instead of using an mechanically driven impeller to generate bubbles, a recirculated stream of clean water is injected into the cell through a nozzle designed to create a venturi effect. Air or gas is drawn into the cell by the venturi and dispersed as bubbles. The injected water flow also agitates the fluid in the cell. Hydraulically induced gas flotation is sometimes referred to as Induced Static Flotation (ISF).
SlPM Deoilinl: Motitrrtl. Et' 93-131.5, Rev 1.1. Nriv 1993. File tirttiie = XI2INI)UC.DOC
P q e 8-12-1
'
Input box
First flotation 'Second flotatioi Third flotation Fourth flotation Discharge box cell cell cell cell
I I
. I
Figure 8.12.2 Schematic diagram of a four cell Monosep hydraulically induced gas flotation package
The advantage of the hydraulically induced design is that it replaces the mechanical driver required for each cell with a single recirculation pump that may be common for a number of cells. This can also improve reliability as a back-up recirculation pump can be provided. To capitalise on this mechanical simplicity, most hydraulically induced gas flotation designs also eliminate the mechanically driven skimming paddles by using alternative weir or level control arrangements. Hydraulically inducing the bubbles is believed to result in lower shear forces in the flotation cell and a more complete distribution of bubbles than an equivalent mechanically induced system. In theory, this should make the hydraulically induced system more effective at capturing dispersed hydrocarbon droplets and more suitable for flotation of flocculated hydrocarbon droplets. However further test work is required to validate this theory. Level probe
Striker plate
Eductor nozzle
H75117/6P
3 "
/J!=(
recirculation
Figure 8.12.3 Schematic diagram of a L'eau Claire hydraulically induced gas flotation cell
Figure 8.12.3 illustrates a cross section of an alternative design for a hydraulically induced gas flotation cell which operates in a pressure vessel. To maximise the working volume of the pressure vessel the
Puxe 8-12-2 SIPM Droilriil: Mmrictl. EP 93-1 71.5 H r v I I . N n v 1993. Filr
11li111e =
XIZINDUC DOC
A disadvantage of hydraulically induced flotation cells is that the recycled water stream reduces the capacity of a given cell size.
Equioment variations Two variations on conventional gas flotation systems are available from Serck Baker. The first is the use of a floating skimmer system. This is claimed to maintain a steady skimming rate regardless of the water level in the cells. This may have some benefits for floating production systems where vessel motion could upset the skimming action of conventional flotation packages. The second is the conversion of a conventional induced gas flotation package to dissolved gas flotation as first applied on the North Sea Beatrice field (ref.2.02.1 .g, 2.02.1.h). The conventional bubble inducers were stripped from the package and gas bubbles were provided by a controlled depressurisation of production water from the 1st stage separator. Claimed benefits are increased throughput and an increase from 20-60% to 70-80% hydrocarbon removal efficiency.
8.12.2.
Performance variables
8.1 2.2.1. Hydrocarbon removal efficiency The hydrocarbon removal efficiency of a single flotation cell is typically in the order of 60 to 70%. Operating experience has indicated that the packaging of four cells in series results in an overall hydrocarbon removal efficiency in the range of 70-99%. Trials at the OWTC indicated overall efficiencies of 80 to 85% with the use of chemical flotation aids. The wide variation in hydrocarbon removal efficiencies experienced in both trials and actual installations highlights the importance of field testing flotation units before selection. Bench scale flotation equipment can be used on site to test the ability of a flotation process to remove dispersed hydrocarbons and to investigate the use of chemicals to improve the flotation performance.
8 95 v
U
p
[u
m
C
90 85
$
U I
75 70 65
80
60 55 50
10
20
30
40 50 60 70 80 90 100 110 120 130 140 Percentage of nominal feed rate (%)
Figure 8.12.4 Relationship between hydrocarbon removal efficiency and flow rate for induced gas flotation
8.12.2.6. Reject stream The froth that is skimmed from the surface of the water contains a significant quantity of water. In general, the reject stream is in the order of 1 to 3% of the total incoming water stream. Some operators have found it advantageous to operate the flotation unit with a reject stream flow rate in the order of 510% of the incoming water stream to maintain a higher skimming rate and allow the unit to quickly recover from high hydrocarbon concentrations in the inlet stream. 8.12.2.7. Chemical addition In many cases, satisfactory hydrocarbon removal performance can be obtained from gas flotation without the use of any treatment chemicals. As with all waste water treatment systems it is preferable not to use chemicals if possible as these will often be discharged with the treated effluent into the environment. However in some cases chemical addition may be required to ensure adequate deoiling performance.
Poae 8-12-4
SIIM
Deoiliiig Maiturtl.
iwiie
= XlllNDUC DOC
SlPM Deoiliiip
Moiiiiol.
Puge 8-12-5
No information is available to indicate whether further investigations have been made into direct sparged gas systems in the E & P environment.
8.12.2.11. Removal of dissolved components Although there appears to be little information available, gas flotation systems can be designed to have some stripping effect on dissolved components in the water. Monosep have been involved with a benzene stripping installation which utilises two flotation units in series. The first unit is a normal flotation cell used to remove the dispersed hydrocarbons from the water. The second unit uses lean hydrocarbon gas to remove dissolved benzene from the water stream, effectively acting as a four stage stripper. A reduction from 180ppm to 5 ppm benzene is claimed. A suitable disposal route for the stripping gas must be identified due to HSE implications.
8.12.3.
Installation/Configuration
8.12.3.1. Process location It is recommended that gas flotation units are used as a second or third stage of a water treatment system. A primary separation stage should be provided upstream, such as a plate interceptor, to provide for removal of suspended solids and slugs of hydrocarbons. 8.12.3.2. Size, Weight and Capacity Table 8.12.1 gives typical sizes of induced gas flotation packages designed for atmospheric pressure operation. The packages are free standing with an integral skid base.
Table 8.12.1 Size and weight of skidded atmospheric gas flotation packages Capacity
(m3W
1 0 68 100 250 500
(m)
(m)
H (m)
Power[l] (kW)
Power[P] (kW)
Notes: [l] Power requirements for mechanically induced gas flotation. [ 2 1 Power requirement for hvdraulically induced gas flotation. . . [3] Weights for complete skidded flotation packages.
7.9 12.3 1 8 . 1
7 . 7 9.8 11.9
2 . 6
1 . 9 2.6 2.8 3 . 3 3 . 8
8.12.3.3. Packaging A flotation cell is effectively a well mixed vessel and thus a certain fraction of the feed stream will short circuit through the cell. To achieve the required hydrocarbon removal efficiency a number of cells (typically four) are combined in series to form a single package. A discharge box is provided after the last flotation cell and is the usual location for water level control instrumentation. An input box can also be used to provide for skimming of free oil and the removal of solids, through this is usually more efficiently performed in upstream vessels. A typical four cell design is illustrated in Figure 8.12.2. Although the majority of flotation packages operate at near atmospheric pressure, designs incorporated into pressure vessels are available from some vendors. Pressurised designs may simplify some design
Puge 8-12-6
SIPM Deoiliiiji Mociucil, EP 93-1315. Rev 1.1, Nov 1993. File nome = XlZINDUC.DOC
Vendors are usually responsible for the sizing and design of flotation packages. As each application and associated water chemistry is different, field trials with trial units or bench scale systems are recommended to ensure that flotation will be effective and to identify the potential need for flotation aids.
8.1 2.5.
Control configurations
Due to the different equipment configurations from different suppliers it is not possible to give a standard control scheme for induced gas flotation systems. However, the following discussions highlight the operation experience obtained from controlling Wemco induced gas flotation systems which have been used in a number of Shell installations.
8.12.5.1. Conventional control A conventional basic control scheme for a flotation package is illustrated in Figure 8.12.5. The water liquid level in the flotation cells is regulated by a level controller located in the water discharge box, while the level in the froth overflow launder is controlled by an independent level controller. The water level in the cells should normally be maintained just below the top of the froth weirs, allowing only froth to flow over the weir. Variations in froth height from cell to cell can be accommodated by altering the height of the weir bars in each cell.
Hydrocaibons
Q
Water
HIt%7aOP
Although this control system will operate satisfactorily under steady conditions, it is dependent upon the generation of a stable froth layer to ensure effective removal of the hydrocarbons from the water. Loss of the froth layer will result in no hydrocarbons being removed via the overflow and all hydrocarbons must then necessarily exit with the water flow. In addition, if the level controller in the water discharge box is only configured for proportional control, upset conditions could result in an offset in the water level. An offset resulting in a low level in the cells will result in less froth overflowing the weirs and a reduction in deoiling performance. 8.12.5.2. MasterMave control system An alternative to the basic control system is the masterklave control system illustrated in Figure 8.12.6. This control scheme was successfully used on the Shell Expro Auk platform, though the flotation unit has since been decommisioned. The basic control scheme was modified by using the output from the level controller in the overflow launder (the master) as the input signal to the water level controller (the slave). The original input signal from the water level in the water discharge was disconnected. As an example of the behaviour of this system, consider the response if lack of froth overflow causes the level in the overflow launder to fall. In this event, the master controller will decrease the signal to the launder LCV to close it further to maintain level in the launder. The same decreasing output signal becomes the input to the water level controller. Perceiving the signal as a decrease in water level the water level controller will partially close the water outlet valve. This raises the water level in the cells and creates more overflow, correcting the original problem. In addition, an overflow from the flotation cells will be maintained at most times.
---+
2ca&ons
Figure 8.12.6 Masterlslave flotation unit control
Water
H7XQb7lP
The advantage of this control scheme is that it can be implemented with existing instrumentation. However it has the disadvantage in that there will be a cycling interaction between the master and slave
I
4
]
I
Hydrocarbons
r.
Water
HI-
This control scheme has the advantage in that an known overflow will be established under all circumstances. This ensures hydrocarbons on the surface of the water are constantly being skimmed from the cell, even in the absence of froth. An example of such a situation would be a large slug of hydrocarbons entering the flotation unit. Such an overload may destroy the layer of froth, resulting in no overflow into the launder. In response the overflow flow controller will raise the level in the flotation cell until the an overflow is re-established, effectively skimming the hydrocarbon from the surface of the flotation cells. The potential disadvantage of this system is that unless the setpoint of the flow controller is manually reset, the reject rate remains constant even for very low feed flow rates. In addition, it is not known whether this control scheme has been successfully implemented in the field.
:-+I
----:
I
I
I
,
,
#
,
I ,
IE
!
. . I
It
HIM26RSP
Water
PUKE
SIPM Deiiiliiig Miiiiitril, EP 93-1315, Rev 1.1, Nov 1993, File i i m i e = RI2INDUC.DOC
Puge 8-12-9
Location
Equipment
A number 01 E 8 P operations
IWemco
USA, Midway Sunset L'eau Claire field Sarawak. Labuan Crude Oil Terminal Sarawak. Labuan Crude oil terminal Chemlink (C) Wemco (W) L'eau Claire (LC) Wemco (W)
Field trlal or insfalled equipment (date of equipment Installation I In brackets) ISummaty of the OpBrating experience with Wemco machines in a number of E 8 P locations. Pilot tests followed by lull scale installation Field trial to consider replacementsto existing Wemco system (Wemco performancein italics). Field trial to consider replacementsto existing Wemco system. (Wemco performancein ifalics).
~~
Reference
.2.2.a
.2.2.b .2.2.c
.2.2.d
USA, Shell Western. Quadricell (0) Fieldtrial to compare two IGF 1984 110 ppm for all Black Bayou, designs. Tested with and without cases Hydrocell (H) the use of chemicals (QC) (HC) Bmnei. Seria oil terminal Wemco and unspecified OAF unit. DAF uses upstream mag. and flocculation. Wemco 9 7 @ l Comparison between dissolved 1982 m gas llotation and Wernco flotation package. Wemcw results in italics (W) (W) 76 md, Operating experience with the Wemco. Laboratoryand field trials comparing Wemco and dissolved gas flotation. Wemco results in italics (W).
I
~= C TABoI-/2
Wemco
.DOC
(a)40 ppm
(a)64%
!x%
(W) 76%
.02.2.e Hydrocell found to be most reliable and best performer. Gives excellent water quality with 4 ppm of flotation aids. Based on lrials a Hydrocelldesign (HC) 4 ppm was purchased. .9.2.a 62% of solids Coagulant and Tests lound the Wemco to be more efficient at removina oil. The DGF unit has a hiaher removal llocculant. removed of solid< however it is not specified 6 the report (W) Flotation aid whether these are being remnved by a flotation or (W) 47% of sdids removed sedimentation process. Not known (QC) 8 ppm Not known Chemicals required to get suitable performance Chemicals had mixed effects (W) Chemicals did not have a significant effect Performancefound to be sensitive to chemical dosage rate and water temperature. Control system altered to improve stability. Report discusses theory. bboratory tests and lield tests in detail. Compares Wemco with dissolved gas llotation units and found Wemco to be more etticient. .2.3.a
mgll
lM)tO299mg/l 141038mg/l
90t095%
50 to 200
1510 125
(W) 10 to 50
Not known
.2.1.1
Table 8.12.2 Page 1 of 2 Deoiling equipment summary table Induced Gas Flotation
- -
Location
Equipment
The Netherlands, NAM. East NetherlandsGas Fields, Drente, Twente Canada, Peace River onshore heavy oil field Canada, Virginia Hills onshore heavy oil field Canada, House Mountainonshore oil field UK, North Sea, Auk platform Brunei, terminal
Oil
Monosep
Field trial or installed Date Inlet Outlet Hydrocarbon equipment hydrocarbon concentration removal concentration (mgil) efficiency (date of equipment installation in brackets) (mgil) 25 72% Equipment trial 1992 90 mgA
Solids handling
U s e of chemicals
Comments
Reference
msn
Not known
10 mg/l flotation Trial results reported through 1993 deoiling aids questionnaire.
Installed equipment (1986) Installed equipment (1989) Installed equipment (1967) Installed equipment (1976) Installed equipment (1981)
77 mgli
5 mgA
50%
80%
1993 5 to 500 mgA 0 to 100 mgA Up to 100% Typically 10 m g l Typically 0 mgl 1993
._--_
.__..
._-__
__.__
No problems
____.
Secondary stage treatment, downstream of skim tank, upstream of sand filters. Secondary stage treatment, downstream of skim tank, upstream of sand filters. Typically good performance with up lo 100 mgA in feed. Etfluent oil concentration Starts to rise proportionally above 100 m@ in feed. lntemals stripped from Wemco due to 'poor performance', Cells now operates as a skim tank
only.
1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire Not
------_-_
_____
____.
...__
20 to 30 ppm of Some problemswith slime and scale build up, poly-electrolyte performance varies directly with throughput at inlet to Wemco Awaiting to be commissioned
_____
.____
_____
SIPM Drnilin~ Munuul, EP 93-1315, Rev 1.1. Nuv 1993. Filenumc = TAB8-12.DOC
1990 Tested from 150 Ranged from 25 Averaged 86% Not tested to 2308 mgl to 288 mq/l lor all concentrations. Efficiency improved to 99% at end of trial with optimised flotation aid.
only a limited nuniber of chemicalaids were tested. referenced EP 90.2641 Correct flotation First series of OWTC trials comparing aid gave large performance of a static hydrocyclone. rotary
__.__
hydmcyclone and flotation unit. Variables tested for flotation included flow rate. oil concentration, droplet size, effect of chemicals. Very big improvement in performance when flotation aid optimised. Efficiency not atfecled by concentration increases or droplets down to 10 urn.
Puxe 8-12-12
Introduction
As with induced gas flotation, dissolved gas flotation assists the removal of hydrocarbon droplets by attachment to rising gas bubbles. The oily froth which forms on the surface of the water is removed by skimming or overflowing to a collection trough. Gas flotation units are generally installed as a secondary stage in a water treatment system. Inert gases, air or hydrocarbon gas are normally used for induced gas flotation. Operation with air is often referred to as Dissolved Air Flotation (DAF). In many cases the use of air is not practical due to the need to exclude oxygen from the process (the presence of oxygen leads to concerns with corrosion, biological growth and explosion hazard aspects). Chemical additives are often used to improve the performance of the flotation process. Gas flotation units are categorised by the method used to generate gas bubbles, either Induced Gas Flotation (IGF) (mechanical and hydraulic) or Dissolved Gas Flotation (DGF). Dissolved gas flotation is discussed in this section. Induced gas flotation is discussed in section 8.12. Figure 8.13.1 illustrates the design of one style of dissolved gas flotation system. Bubbles are generated by saturating a liquid stream with gas, typically at a pressure of 3 to 6 barg. As the liquid is depressurised, the gas is released as fine bubbles. The rising bubbles can attach themselves to hydrocarbon droplets and solid particles and float them to the water surface from where they can be removed.
Frothscraper Clean water launder ( 3 6 0 ' )
Water + flocculants
Distribution
Flotation gas
Saturator vessel
Recycle pump
2 4
The main advantages of the dissolved gas process over induced gas systems is the relatively gentle method of generating the gas bubbles. The absence of high shear forces in the flotation cell allows DGF to handle flocculated feed streams without breaking up the flocs. Opco trials have indicated that for unassisted water treatment an induced gas flotation system is more efficient for removal of hydrocarbons than a dissolved gas flotation system. However, the dissolved gas system has been found to be more efficient in removing fine solids. As a result, a dissolved gas flotation system would often be recommended over an induced gas system for applications requiring solids removal or where a pre-flotation flocculation stage is used or required. Figure 8.13.1 illustrates the use of an stirred vessel as the flocculation stage for the DGF system. A coagulant stage can be used before flocculation to assist the gathering of the dispersed hydrocarbon droplets into microflocs. The flocculant then gathers the microflocs into larger flocs. Coagulation and flocculation are discussed in more detail in section 8.4. Treatment chemicals can also be used to assist the removal of solids, by helping to bind the solids into the flocs, or by altering the surface chemistry to make the solids more hydrophilic and thus more likely to be gathered by the flotation bubbles. Figure 8.13.2 illustrates a common variation of dissolved gas flotation system, the use of a plate pack to
SlPM Deoilinp M(iiiuo1, EP 93-1315, Rev 1.1, Nov 1993. File iiiiiiir = XI3DISS.DOC
Puge 8-13-1
I
Clean water
c*TJy
Serpentine pipe
Flotation gas
-.
pump
KlYldyIlP
Figure 8.13.2 Dissolved gas flotation unit with plate interceptor and serpentine pipe flocculator
The plate pack provides a laminar flow regime which allows small hydrocarbon droplets, flocs and gas bubbles to be separated from the water stream. Also illustrated is a serpentine pipe flocculator. This type of flocculator operates in plug flow, using the natural flow turbulence and the residence time in the serpentine pipe system to promote flocculation. The stream to be saturated with gas can be the full feed stream, a proportion of the feed stream or a recycle stream from the discharge of the DGF unit. The recycle stream system is the most common, having the advantage of using a clean water stream in the saturation system (Le. no solids or hydrocarbons to contaminate the saturation equipment) and ensures that the largely hydrocarbon free recycle stream, not the feed stream, is exposed to the shear forces experienced during the depressurisation of the gas saturated stream. This is particularly important in ensuring the maximum hydrocarbon droplet or floc size enters the flotation cell.
8.13.2.
Performance variables
8.13.2.1. Typical p e r f o r m a n c e
90% or higher with a suitable flocculation stage. The use of flocculation may also assist the removal of
Field trials have indicated that a DGF unit can achieve a hydrocarbon removal efficiency in the order of
If a flocculation stage is not used, an induced gas flotation system as described in section 8.12 would generally be recommended over a DGF unit.
- 70 - 60 - 50
-40 -30
- 20 - 15 - 10
0 . 0 1 0
10
I
Fi
20
30
40
60 Temperature C
50
70
80
90
100
1- 0
The amount of gas released during depressurisation will be a function of the difference in gas solubility between the pressurised and depressurised water and the amount of gas that can actually dissolve into the water in the saturator. Due to the short contact time, equilibrium gas solubility will not be achieved between gas and liquid in the saturator. A saturation efficiency in the order of 70% can be expected for a simple saturation vessel, increasing to the order of 90% for a more efficient saturator using internal packings or a pump based saturator.
It should be noted that most of the flochubble contact will often take place in the inlet piping or inlet chamber of the DGF where the bubble concentration is highest. The residence time in the inlet system is often very short, in the order of 20-30 seconds. Outside of the inlet system the bubble concentration and chances of droplethubble contact fall rapidly. Thus most of the hydrocarbonlsolids removal is accomplished in the inlet system with the bulk of the residence time in the DGF allowing for rising of the flocs and bubbles.
SIPM Deoilinl: Menuol, &P 93-1315, Rev 1.1. Nnv 1993, File nome = N13DISS.DOC
Puge 8-13-3
It is recommended that the upstream primary treatment stage is designed for the removal of the larger, rapid settling solid particles. With the correct addition of flotation chemical aids, the remaining fine solids should be able to be successfully removed by the flotation process.
8 . 1 3 . 3 .
InstallationKonfiguration
- -- -- - Pressure retention
Oily scum
effbent
lank
HIWw24P
e$$$
Flocculation chamber
effluent
Pressure retention tank Figure 8.13.5 Split flow operation Oily scum
W75m8)2SP
,
I
I
Flocculation
$&!$;
~ l . chamber
effluent ~
t, A .
Pressux retention
-w T!
I
H75m6R6P
One potential source of a gas saturated liquid stream is the process itself. This technique was applied on the North Sea Beatrice field in the conversion of a conventional induced gas flotation package to dissolved gas flotation (ref.2.02.1.g, 2.02.1 .h). The conventional bubble inducers were stripped from the package and gas bubbles were provided by a controlled depressurisation of production water from the 1st stage separator. Claimed benefits are increased throughput and 80% hydrocarbon removal efficiency. 8.13.3.3. Size, Weight and Capacity Due to the wide range of potential designs it is not possible to give typical sizes and weights for dissolved gas flotation equipment.
8.13.4.
Design guidelines
Vendors are usually responsible for the sizing and design of flotation packages. As there is no standard design for dissolved gas flotation units, no specific guidelines may be given.
8.13.5.
Operational considerations
8.13.5.1. Intermittent skimming The API guide to water treatment claims one operating installation found an improvement in DGF performance by operating with intermittent skimming. This was believed to allow the formation of a stiffer, relatively stable and more concentrated foam/scum layer on the water rather than damaging the foam/scum layer with continuous skimming.
SlPM Deoilinl: Mtriiicnl, EP 9.7-1315. Rev 1. I. Niiv 199.7, Filc ililiile = X131)ISS.I~OC
Puge 8-13-5
P U ~8-13-6 C
SIPM Droilinx M(inuri1. EP 93-1315, Rrv 1.1, Nov 1993, Filr ncime = Xl3DISS.DOC
I I
P U ~8-13-8 C
StPM Drriilinp M(iiwfi1,EP 93-1315, Rrv 1.1, NIW 1993, Filr niime = X13DISS.DOC
Introduction
As with most deoiling equipment, the hydrocarbon removal efficiency of the filter will be a function of the hydrocarbon droplet size in the feed. However for most applications media filters can produce a water effluent with a hydrocarbon content of less than 10 mg/l dispersed hydrocarbons, often achieving less than 5 mg/l.
It is important to note that media beds do not operate by surface filtration. Surface filtration is the separation mechanism where the particles or droplets to be filtered from the water removed become wedged in the spaces between the grains of media. Surface filtration in a deep bed filter is undesirable as it will quickly result in blockage of the top layer of the bed and the capacity of the subsequent layers of the media bed will not be effectively utilised. The pore openings between the granular media grains are relatively large compared to the suspended particles, allowing the particles to pass into the bed of the filter. Inside the bed the suspended particles become trapped by first intercepting, then attaching to the media. Thus the suspended particles and droplets in the feed stream are removed within the body of the media bed, not on the surface.
Feed distributer
Anthracite media layer Garnet media layer Clean water outlet Filtrate collection
SIPM Drorlrnji Moiirrrtl. EP 93-1315, Rev I 1. NIIV 1993. Frlr iirririe = 814DEEP DOC
P q e 8-14-1
8.14.2.
Performance variables
Puae 8-14-2
SIPM Deoilinji Mwirurl, EP 93.1315. Rev 1.1, Nuv 1993. File ntrrne = X14DEEP.DOC
10
15
20
Particle size (pm) Figure 8.14.2 Typical separation performance of a multimedia filter
However, the performance of a filter must be considered in relation to both particle removal efficiency and overall filtration efficiency. Particle removal efficiency is a measure of how efficiently a filter removes a particle or droplet, regardless of the throughput through the filter. Filtration efficiency takes the flow rate through the filter into consideration. For example, large solid particles or droplets entering a media filter will be quickly removed in the uppermost layer of the media bed, leading to surface filtration. The surface layer will be very efficient at removing incoming particles, hence will have a high particle removal efficiency. However, the actual flow rate through the surface layer will be restricted, resulting in a low overall filtration efficiency. This behaviour is illustrated in Figure 8.14.3. It can be seen that above a certain ratio of particle diameter to media diameter, surface filtration effects will dominate and although the particle or droplet removal efficiency will continue to rise, the overall filtration efficiency will fall.
Thus, for a given media grain size, there will be an optimum feed particle or droplet size that will be efficiently filtered without inducing surface filtration. As an indication, for a media Particle diameter I Filter grain diameter bed of spherical particles, the largest particle H75026127P Figure 8.14.3 that can pass into the bed has a diameter of Particle removal efficiency and about one seventh (117) of the diameter of the filtration efficiency vrs ratio of feed media particles. Thus the feed to a filter particle or droplet size to filter media size consisting of 0.5 mm sand particles should not contain particles or droplets larger than 70 microns. In general it is recommended that particles or droplets larger than 100 pm are not allowed to enter the filter. This particle size corresponds to the size of solid particle or oil droplet that is readily removed by relatively simple upstream equipment such as a plate pack interceptor.
Puge 8-14-3
SIPM Droilinh. Mtri~rtcrl. EP 93-1315, Rev 1.1, Nvv 1993. Filr nomr = Xf4DEEP.DOC
8.14.3.
InstallatiotVConfiguration
As media filters are not tolerant of high hydrocarbon or suspended solid concentrations in the feed stream they are generally used as the second or third stage of water treatment. As previously discussed, it is recommended that upstream equipment should be designed to remove hydrocarbon droplets and solid particles larger than 100 pm. Course strainers (100 pm) should also be installed on the backwash system to prevent blockage of the filter distribution and collection systems.
8.14.3.2. Pressure drop The pressure drop across a clean media filter is typically in the order of 0.4 bar. When used for filtering solid particles the pressure increase over the filtration cycle is normally in the order of 0.3 to 1.4 bar. When the filtration cycle is dominated by hydrocarbon removal, the pressure increase is generally at the low end of this range when hydrocarbon breakthrough into the filtrate occurs. 8.1 4.3.3. Packaging Media filters are typically packaged into vertical pressure vessels. Suitable distribution and collection internals are required to ensure an even distribution of the water flow though the media bed. One standby filter should be provided to be brought on-line when other filters are backwashed or shutdown for maintenance. When specifying a filtration system, it should be remembered that in addition to the filter vessels themselves, provision may be required for a clarification tank for the backwash water and a storage tank to store clean filtered water to perform the backwash.
0) .-
- 200 g
(u
3 250
C
p .E
150
0" 100
50
0
0
100 200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
Capacity (mYh)
Figure 8.14.4 Operating weight of dual media or crushed nut deep bed filtration systems
iwiiie
= 814D12Y.DOC
Puge 8-14-5
Design guidelines
The following guidelines can be used for indicative sizing of downflow multimedia filters for the filtration of oily water. Higher flux rates are possible for sea water filtration duties (see SlPM Water Injection Manual, Report EP-63600). Guidelines for crushed shell filter media designs are given in section 8.14.7.
0
Flux rate through filter: 20 40 (m3/h)/m2 Accumulated hydrocarbon capacity of filter bed before cleaning: 40 kg/m2 Accumulated solids capacity of filter bed before cleaning: 20 kg/m2 Maximum recommended continuous hydrocarbon feed concentration: 30 - 50 mg/l Multimedia backwashing water flow: 40 (m3/h)/m2 for 10 to 30 minutes
When filtering oily water, the dirty backwash water is generally recycled to the process after the hydrocarbons and solids are removed. The capacity of the filtration package has to be sufficient to accommodate this recycling flow. The frequency of backwashing should be such that there is sufficient time in the clarification tank to allow solids and hydrocarbons to settle from the backwash water and for clarified water to be pumped away before the next filter backwash.
Figure 8.14.5 illustrates a typical control scheme for a deep bed filter system. Each filter is flow controlled by a flow meter and control valve on the outlet of the filter. This control system should ensure that all filters are operating with the same load. This is particularly important when a clean filter is brought on line, otherwise the clean filter will tend to rob the flow and over-flux, shortening the subsequent filter cycle.
b
n76mmw
8.14.6.1. Backwashing control During the backwash cycle the media bed is fluidised. The degree of fluidisation is a function of the density and the viscosity of the backwash fluid, both of these variables being functions of the backflush fluid temperature. The optimum backwash flow rate to give sufficient fluidisation without excessive media loss should be determined for the range of backwash fluid conditions, The backwash fluid flow rate should be measured and controlled at the appropriate rate. If backwash fluid conditions are likely to change significantly (e.g. wide temperature variations) then automatic adjustment of the backwash flow rate setpoint may be warranted. 8.1 4.6.2. Media loss The rate of media loss from the filter is a function of the frequency of backwashing and proper control of the backwash cycle. Media is also lost by attrition of the media particles. Typical media loss is in the order of 10% per year. 8.14.6.3. Operating experience A large number of deep bed media filters are commonly used throughout the petroleum industry for the filtration of sea water for water injection. However installations for the filtration of oily water are not as common. Table 8.14.1 summarises the operating experience with deep bed media filters for the treatment of oily water for a range of Shell installations and trials.
P U ~ 8-14-6 C
SlPM Deoilinx Mmurrl. EP 93-1315, Rev 1.1, Nov 1993, File ncrme
= N14DEEP.DOC
8.14.7.1. General
Crushed nut shell filters are a form of deep bed media filter, utilising crushed walnut or pecan nut shells as the filter media. They are of particular interest to the filtration of oily water due to the hydrophilic nature of the filter media which ensures the filter media is preferentially water wetted. This allows the hydrocarbons that are filtered from the feed stream to be relatively easily removed during backwashing. Backwashing is performed using the unfiltered feed stream as the fluidising medium, eliminating the requirement for a storage tank to store filtered water for backwashing. The flow rate of backwash water is significantly lower than for conventional deep bed filter designs, minimising the size of additional facilities required to deal with the dirty backwash water.
No additional media cleaning facilities such as gas scouring or chemical addition are required. As the media is efficiently cleaned there should be no requirement for media replacement except to cover a 1015% annual media loss due to attrition.
At the time of writing there are no crushed nut media filters being used for the filtration of sea water. SIPM are planning to evaluate this aspect in 1994 to determine whether a crushed nut shell filter could be used for sea water filtration in the early years of a field development, then be switched to produced water service as the field matures.
8.14.7.2. Hydromation
The Hydromation filter is illustrated in Figure 8.14.6. During the filtration cycle the filter acts as a normal deep bed filter, using crushed walnut shells as the filter media. During the backwash cycle the filter is shut in and the media scrubber pump used to fluidise, then circulate the filter media downwards through the external media scrubber. The media scrubber contains a wedge-wire strainer that allows small particles and hydrocarbons to pass to the backwash discharge, while the filter media is returned to the filter vessel. The turbulence and collisions generated during the backwash recirculation cleans the filter media.
t
1
1P
I
Air/gas vent
Access hatch
vation ports
After the backwash the flow through the filter is reversed and the filter bed reforms. The filter is then operated for a short period on recycle to wash the contaminated backwash water out of the filter bed. The filter is then clean and ready to be brought back on line.
-rC Dirtywater
inlet
Contaminant discharge
IC-
Drain
-.+.
Figure 8.14.7 Wemco Silver Band crushed shell deep bed media filter
n water IC outlet
The backwashing and media cleaning system is similar to the Hydromation filter with the clean water outlet valve shut and the filter media recirculated by a pump past a separator screen. The screen allows the solids and hydrocarbons to exit the filter but retains the filter media inside the vessel. The Silver Band filter has the separator screen built inside the filter vessel itself. After the backwash the recirculation is stopped and the filter bed reformed. The filter is then clean and ready to be brought back on line. The Wemco Silver Band filter has been tested at the OWTC. The full test report (EP 91-2152) can be obtained from SIPM on request. The filter was found to consistently achieve in the order of 10 mg/l hydrocarbon in the effluent from a 200 mg/l feed stream.
P U ~8-14-8 C
SIPM Duoilinji Mcrnud, EP 93-1315, Rev 1.1, Nov 1993, File ncrmr = 814DEEP.DOC
SlPM Deoiling Mrtnuctl. EP 93-1315, Rrv 1.1. Nov 1993, File nonrr = XI4DEEP.DOC
Puae 8-14-9
Location
Equipment
Oman. Mina al Fahal Hydromation oil terminal and Marmul, Suwaihat and Qarn Alam onshore production stations Oman, Mina al Fahal oil terminal and Manu1 onshore production station The Netherlands. Schoonebeck Spain, Shell Espana San Carlos de la
Inlet Outlet Hydrocarbon Date Field trial or Installed equipment hydrocarbon concentration removal (date of equipment Installation concentration (rngl) efficiency in brackets) (mgl) (MaF) 76 to 95% Equipment field trials, results 1992 (MaF) 32 to 154 (MaF) 5 to 17 (M) 157 (M) 24 (M) 85% given lor Mina a 1 Fahal (MaF), m 6 . 9 w Lsm!.YQ Marmul(M), Suwaihal & and (a) 3 to i o (a) 85 to 95% Qarn Alam (Q). Note that all (Q) 54 to 62 results are given in ppmv 1992 (MaF) 38 m g l
(M) 4 14 mg7
Solids handling
Use of chemicals
Comments
Reference
InPlant lilter Equipmentfield trials, results using given lor Mina a 1 Fahal (MaF) oleophilic filter and Marmul (M media Hydromation Field tnals with Hydromation filter. Field trial on tanker vessel 'Delta', Castellon field
(MaF) 4 mgl
(M) 55 m y l
(MaF) 89%
(M) 85%
lot used Typical for all fields Inlet 9 lo 69 m d Outlet 7 to 30 mgfl 11 to 71% 01 solids removed (MaF) 34 rngl lo lot used 16mgnie 53% reduction
4 pm range and 95% of particles greater than 4 pm. It is suspected that lor one location corrosion
inhibitor reduced the performance of the filter, through not in other locations. In this one case the media had lo be replaced. During the MaF trials. best results were obtained 2.7.2.k when lresh water was used lor backwashing. Unit suffered from mechanical problems. Mechanical problemsconsidered reason lor high Marmul oullel concentrations, lor some periods outlet oil concentrationsless than I O mg!l were obtained. 2.7.2.h Excellent performance lrom trial unit, oil concentrations reduced from 100 or 200 ppm lo lower than 1 ppm. Performance01 the Mer was found to improve with 2.7.2.1 the addition 01 5 lo 10 ppm 01 Willloc polymer. Filter design allows for the continuous draw on and 2.7.2.b cleaning 01 the filter media. However it was tound that the oil concentration in the outlet water was loo variable. 1993deoiling Performance of sand filter deteriorated over a period 01 2 years. Improved abet chemical cleaning questionnaire 01 filler media 1993 deoiling Water disposed of in disposal wells. Initial target was less than 3 m g l oil. Disposal lormation found questionnaire to be tolerant thus performanceof lilter has not been optimised. This reduces use of chemicals.
0 to 4 mgA
Average 01 95% I O to 74 ppm solids. reduced to 0 4 to 6 ppm Average 01 79% Not known
lot used
Hydromation
Denmark, Fredericia Dynasand relinery continuous /filter onshore oil field heavy oil field
kA%
Not relevant
80%
IAveraoe removal 00 ppm poly!lectrolyte of TSS - 67% Not known Typically 65 mg/ in feed
401 used
1 rngl
mdl
Typically 15 rngl
tOlo170mgl
Jot used
SIPM Droiling Monuul, P 9.1-11115. Rev I .I. N w 1993, File nome = TABX-I4
,oc
Table 8.14.1 Page 1 of 2 Deoiling equipment summary table Deep Bed Media Filtration
Location
Columbia. Dina onshore oil field The Netherlands, NAM. East NetherlandsGas Fields, Drente, Twente Brunei, Seria oil terminal OWTC
Field trial or installed Date Inlet Outlet Hydrocarbon Solids handling Use of equipment hydrocarbon concentration removal chemicals efficiency (date of equipment installation concentration (mgn) in brackets) (in@) L'eau Claire Installed equipment, (1985 and 1993 10 to 100 mgl 1 to 8 mgl 94% Typically 20 mgl 1 ppm 01 polyin feed electroiyle added and 1991respectively) Typically 50 mgl Typically 3 mgl to filter feed Depremont 7 to 40 mg/l Not relevant Normally20 to No chemicals Wemco Silver Installed equipment (1992) 1993 10 to 250 mgl Band Typically 25 mgl Typically 16 m@l 25 mgl in leed. used may of 50 mgA Equipment
Comments
Reference
1993 deoiling river. Filters perform well given that upstream questionnaire facilities are undersized. Thought that filter requires higher feed pressure to 1993deoiling ensure bed compaction and better performance. questionnaire
Serck Baker
InstalledeauiDment (1985) . . . ,
Tvoicallv 5 mail
I. I
Not relevant
I.
Not known
See comments
Coaaulationand flocculation chemicals used in ]upstream flocculatiodflotation unit. Filter optimisedat 200 mg/l in feed, consistently gave below 15 mgl in product. Performance generally good. Presence of demulsifier caused very poor performance(D 100 mgll in product) but concentrationof demulsifier was far higher than the residual levels of demulsifier that would IvDcally .. . be lpresent in the feed.
causedvery poor increased wiih solids, however perlormance. See comments not fully investigated
Table 8.14.1 Page 2 of 2 Deoiling equipment summary table Deep Bed Media Filtration
PURC8-14-12
SIPM Deoilitig Motiud. EP 93-1315. Rev 1.1. NIJV199.9, File tiotne = XI4DEEP.DOC
8.15.2.
Performance variables
8.15.2.1. Hydrocarbon droplet and solid particle size Cartridge filters are capable of removing hydrocarbon droplets and solid particles down to very small sizes. A common performance specification is 98% removal of particles down to 2 pm. Users should be aware of the difference between absolute and nominal filter ratings. An absolute filter will ensure all particles larger than the absolute rating will be removed by the filter. A nominal rating indicates the median particle size removed, however a percentage of larger particles may still pass through the filter. Cartridges are available with absolute ratings down to 0.6 pm.
8.1 5.3.
8.15.3.1. Process location As previously discussed, due to the cost of replacing cartridges, cartridge type filters are normally used at the end of the water treatment process where the hydrocarbon and solids loading is very low. In many cases, they are used as guard filters to provide a last line of defence in case of failure of upstream deoiling equipment. 8.1 5.3.2. Packaging To provide the required filtration area, a number of cartridges are packaged together on a tubesheet and placed in a vertical pressure vessel. The system should be designed for simple and quick replacement of
8.15.4.
Design guidelines
The sizing of a cartridge filtration system will vary significantly with the filtration rating of the filter elements. Relatively coarse filter elements will have a much higher flux rate than finer filter elements. Vendors should be contacted to determine the characteristics of suitable cartridges.
Once the pre-coat layer is established the oily feed stream can be introduced to the filter. A slurry of filter aid (known as body feed) is continually added to the feed to ensure that the filter surface is continuously renewed and remains permeable. The function of the filter aid is to provide a permeable surface structure to allow the continuous accumulation of solids and hydrocarbons. Without filter aid the filter would be quickly blinded by the accumulating solids and hydrocarbons in the filter cake. The end of the filtration cycle is reached when the differential pressure across the filter reaches a predetermined maximum or when there is no more physical space inside the filter to deposit the filter cake of solids, hydrocarbons and filter aid. The filter is taken off line and the accumulated filter cake removed from the filter. The filter cake can be removed from the supporting mesh by a variety of methods such as water sprays, backwashing, pneumatic pulses etc. Once the filter cake is removed and the filter is clean the filtration cycle can be restarted. Normally, dispersed hydrocarbons are difficult to filter as the hydrocarbon droplets will deform under pressure and blind the filter. The advantage of the pre-coat filter is that the body feed helps maintain the permeability of the filter cake under these conditions. The main disadvantages of the pre-coat filters is the inconvenience of handling the dry and slurried filter aid, the operating cost of purchasing the filter aid and the potential disposal problem of the oily filter cake.
8.16.2.
Performance variables
p y
c
5 L
(u
i i
c
8.16.3.
Installation/Configuration
8.16.3.1. Process location As pre-coat filters are not tolerant of high hydrocarbon or suspended solid concentrations in the feed stream they are generally used as a final stage of water treatment. 8.16.3.2. Guard filters When using pre-coat filters there is always a possibility of some of the pre-coat material passing through the filter. It is recommended that guard filters (typically cartridge type) are installed to protect the downstream environment from poor pre-coat filter performance or any accidental breakthrough of filter aid. The guard filters will also give an immediate indication of problems with the pre-coat filters by a rapid rise in differential pressure.
8.16.4.
Design guidelines
The following guidelines can be used as initial design parameters for a pre-coat filtration system. Flux rate through filter for produced water: Diatomaceous earth bulk density: Perlite bulk density: Typical diatomaceous earth pre-coat: 1.2 - 2.5 (m3/h)/m2 Dry powder, 110 - 240 kg/m3 Wet filter cake, 240 - 320 kg/m3 Dry powder, 60 - 90 kg/m3 Wet filter cake, 110 - 130 kg/m3 2 of filter area 100 - 150 kg / 100 m
8.16.5.
Operational considerations
8.16.5.2. Maintenance of flow The pre-coat and filter cake must be held on the mesh supports at all times by maintaining a positive flow through the filter, particularly when switching from the pre-coat cycle to the filtration/body feed cycle. In the event of loss of positive pressure on the filter cake (e.g. power failure) the filter contents will have to be dumped and the filters re-coated before resuming filtration.
PURC
8-16-2
iifiiiw
= X16DIAT DOC
P U ~ 8-16-3 C
P U ~ 8-16-4 C
SIPM Deiiiliiig Miiiircol, EP 93-1315, Rev 1.1. N ~ I 1993. V File nilme = X16DIAT.DOC
MEMBRANES
Introduction
Membranes act fundamentally like filters. Membrane processes cover microfiltration, ultrafiltration and nanofiltration. Microfiltration and ultrafiltration use porous membranes and separate on the basis of size, with droplets or particles larger than the pore size not passing through the membrane. Nanofiltration uses non-porous membranes and separates on the basis of selective solution and diffusion of a species through the membrane Figure 8.17.1 illustrates the typical operating ranges of the various membrane filtration processes.
0.00001
0.0001
0.001
0.01
0.1
10
100
1000
10000
To separate hydrocarbons from water, membranes are operated in a cross flow configuration with the oily water flowing across the membrane surface. The cross flow configuration helps minimise fouling by sweeping hydrocarbons and solids along the membrane surface. The water at the membrane surface will preferentially pass through the membrane, producing a clean water permeate. The remaining concentrated hydrocarbon/water stream is known as the retentate or concentrate. As illustrated in Figure 8.17.2, membrane systems are normally operated with a recycle stream which can be up to 20 times the feed rate. This raises the hydrocarbon concentration of the stream feed across the membrane surface and reduces the flow rate of the reject stream that is withdrawn to remove the accumulating hydrocarbons. While membranes for oily water clean-up show considerable promise, the generally rapid decline in flux rates due to fouling and variable results in membrane cleaning have hampered their application..
H75117/11P
Treated water
I%ed
Recycle
- Reject stream
4
8.17.2.1. Hydrocarbon droplet size The pore sizes for microfiltration or ultrafiltration membranes is very small and will not allow hydrocarbon droplets to pass. However water (and dissolved hydrocarbons) will pass through the pores. As illustrated in Figure 8.17.1, very small hydrocarbon droplets can be separated from a water stream with a microfiltration or ultrafiltration membrane. Nanofiltration membranes are non porous and are thus completely independent of hydrocarbon droplet size. However, hydrocarbons can still potentially pass through the membrane by physically dissolving into the membrane and diffusing through. 8.1 7.2.2. Inlet and outlet hydrocarbon concentrations The tests at the OWTC indicated that the membranes were not particularly sensitive to inlet hydrocarbon concentration. Increasing the inlet hydrocarbon concentrations from 50 mg/l to 1000 mg/l resulted in rises in permeate concentration from the order of 5 mg/l up to a range of 10 to 15 mg/l. This performance indicating an ability to maintain a low outlet hydrocarbon concentration when faced with high inlet hydrocarbon concentrations is very encouraging. It should be noted that, as membrane systems typically utilise recycle streams, the concentration of hydrocarbons within the recycle loop will be already be significantly higher than the initial feed concentration. High levels of hydrocarbons in the feed may result in more rapid fouling, lowering the membrane flux rate and shortening the membrane life. To minimise the need to clean the membrane and to maximise the working life of the membrane, the concentration of hydrocarbons in the feed stream should generally be kept as low as possible. Membranes should be protected from slugs of pure hydrocarbon. When the reaction of the membranes to hydrocarbon slugs was tested at the OWTC, the membranes showed relatively small changes in the permeate hydrocarbon concentration, however, for several membranes the flux rates through the membranes dropped dramatically until the slug was cleared. 8.1 7.2.3. Dissolved hydrocarbons By definition, porous membranes should not have any effect on the levels of dissolved hydrocarbons in the permeate. In many cases, the dissolved hydrocarbon content in the permeate may be higher than the feed due to the recycle stream building up higher concentrations of dissolved hydrocarbons within the membrane unit. In some cases, porous membranes have achieved reductions in dissolved hydrocarbons. This effect may be related to the concentration of dispersed hydrocarbons remaining in the retentate altering the solubility of the hydrocarbons in the water phase. This effect may not be consistent enough for the reliable reduction of dissolved hydrocarbons. Non-porous membranes in which the water dissolves into the membrane may achieve some separation of dissolved hydrocarbons on the basis of different rates of diffusion through the membrane. However, to date, trials to specifically investigate the removal of dissolved hydrocarbons alone (as opposed to the numerous trials with dispersed hydrocarbons) do not appear to have been conducted. The SDI membrane design appears to have some potential for the separation of dissolved hydrocarbons and is being evaluated by Shell Expro. Membranes can potentially be used to assist the removal of dissolved hydrocarbons as part of the pervaporation process. This process is discussed in more detail in Chapter 9. 8.17.2.4. Membrane flux The flux across a membrane is a function of a number of variables, particularly pore size, water viscosity and pressure drop across the membrane. Fouling of the membrane will result in a gradual deterioration in the flux rate. At the current stage of development it is unlikely that vendors could provide a realistic flux rate given the operating conditions and allowing for fouling over the life of the membrane. The design of membrane systems must be based on a stable long term flux rate that can be expected from the membrane over a long period of operation. Current stable flux rates are too low to be economic when compared with other equipment. Flux rates of new, clean membranes or when tested with water
P U ~ 8C 17-2
SlPM Dcoiliiil: Miirircnl. EP 93-1315, Rev 1.1. Nov 1993, File nnrnr = X17MEMB.DOC
~~~~
8.17.2.5. Temperature
In general, the flux rate through a membrane will improve significantly at higher temperatures. This variation in flux rate will have a significant impact on the required membrane area.
8.1 7.3.
8.17.4.
Membrane trials
Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd, Phase I, 15 April 1991, EP-no. 91-1017 The following four membranes were examined in the Phase I trials: Alcoa Petrolox, SDI, Stork-Wafilin and X-Flow. The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, concentration, droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals, gas breakout, and scale forming compounds.
Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd, Phase II, 20 September 1991, EP-no. 91-2152 The following three membranes were examined in the Phase I trials: WL Gore, Schelde Delta and SDI (modified since Phase I trials). The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, oil droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals and scale forming compounds.
9.1.
INTRODUCTION
In many E & P operations, particularly offshore, both regulations governing hydrocarbon discharges and deoiling equipment design are based on the removal of only insoluble dispersed hydrocarbons from waste water. However, as illustrated in Chapter 2, waste water from hydrocarbon production facilities may contain significant quantities of dissolved hydrocarbons. In many land based installations, particularly in the refining and manufacturing industries, discharge regulations and environmental considerations frequently require the removal of both dispersed and dissolved hydrocarbons from effluent waters. There is speculation that similar standards may be applied to the discharge waters from E & P operations, including offshore installations. The following sections introduce and discuss the range of equipment available for the removal of dissolved hydrocarbons. Unlike the removal of dispersed hydrocarbons where the hydrocarbon and water phases are physically separated, the majority of the techniques used for the removal of dissolved hydrocarbons will generate a third stream such as stripping gas, liquid or solid adsorbents or sludge. The design of any system for the removal of dissolved hydrocarbons must allow for the handling and processing of these additional streams.
Waste water is often saline and contains many contaminants which will affect the solubility of hydrocarbons.
At some stage in the process the waste water has usually been in close contact with a hydrocarbon phase. Water soluble hydrocarbons will still have an affinity for other hydrocarbons and the level of dissolved hydrocarbons in the water depend on how the hydrocarbons partition between the two phases.
The actual dissolved hydrocarbon concentration is a key parameter required for the design of equipment for the removal of dissolved hydrocarbons, yet is often not known at the design stage. A number of methods can be used to determine the probable dissolved hydrocarbon concentration. Water samples taken during well tests can be analysed to determine the dissolved hydrocarbon content. This can provide valuable information for subsequent design. The well test operating conditions should be clearly noted. From hydrocarbon and water analyses, computer simulation may be used to predict expected the levels of dissolved hydrocarbons. The accuracy of such prediction is typically in the order of f 30%. Samples of produced hydrocarbons and produced water can be used in laboratory trials to investigate the levels of dissolved hydrocarbons. While effects such as ageing will reduce the accuracy of laboratory tests, they can be used to give broad confirmation of other prediction methods. Methods for estimating the concentration of dissolved hydrocarbons in water are presented and discussed in Appendix J. KSLA have conducted a number of trials to investigate the solubility of hydrocarbons in water for a planned gaskondensate development. , The following results were found.
0
A relatively good correlation was found between predicted dissolved hydrocarbon levels and measured hydrocarbon levels, particularly when predicted results were compared against the levels of dissolved hydrocarbons from existing platforms.
The solubility of hydrocarbons in water was found to decrease with increasing water salinity.
No significant variation of the hydrocarbon solubility in water was measured when increasing the water pH from 4.5 to 7.0. No significant variation of the hydrocarbon solubility in water was measured when increasing the water temperature from 20C to 50C. The presence of methanol in the water phase was found to significantly increase the solubility of hydrocarbons in the water. The presence of corrosion inhibitor was found to significantly increase the apparent solubility of hydrocarbons in the water phase. However it is not sure whether the measured hydrocarbons were actually dissolved in the water or were present as an emulsion of very small dispersed hydrocarbons stabilised by the corrosion inhibitor.
P u p 9-2-1
SlPM Deoilinx Morlrtrrl. EP 93-1315. Ruv I. 1. Nov 1993, File II(IIIIP = 901902,DOC
GAS STRIPPING
Introduction
Gas stripping of volatile compounds from water in a column is a relatively well established procedure. The basic design of a stripping process (using air as the stripping medium) is illustrated in Figure 9.3.1. Water and the stripping gas are counter-currently contacted in a packed column where the volatile components migrate from the water phase into the stripping gas. The most common stripping gases used are air, nitrogen and lean hydrocarbon gas. Steam stripping is discussed separately in section 9.4. The advantages and disadvantages of the various types of gas stripping mediums are summarised in Table 9.3.1.
H75117mP
r.-----
VOC'S
Feed
Air
I
It must be noted that stripping does not eliminate dissolved hydrocarbons, only transfers them from the water stream to the gas stream. A suitable route must be available to process or dispose of the stripping gas.
9.3.1.2.
Nitrogen stripping Nitrogen stripping operates in the same manner as air stripping, however does not incur the disadvantages introduced by the presence of oxygen. The major disadvantage of nitrogen stripping is the cost of generating nitrogen. The volume of nitrogen required is typically in the order of 30 times the volume of water to be treated and unless a suitable source of cheap nitrogen is readily available nitrogen stripping is not competitive with alternative stripping methods. The disposal of the waste nitrogen gas must also be considered. If venting of the waste gas is acceptable, normal vent lines may be used as nitrogen does not create an explosion hazard. However, the health and environmental implications of the vented gas must be carefully considered. If venting is not acceptable the waste gas must be cleaned by adsorption or incineration.
iiiiriir
= 9O.<STRIt'.OOC
P q e 9-3-1
Advantages
1. Air is cheap and abundant.
Disadvantages
1. Explosion risk due to presence of oxygen. 2. Organic and biological fouling due to presence of oxygen. 3. Potential corrosion problems due to presence of oxygen. 4. Only transfers problem from water stream to air stream
Advantages
1. Eliminates explosion risk by excluding oxygen. 2, Can use normal vent system. 3. Eliminates oxygen associated corrosion and fouling.
Disadvantages
1. Cost of supplying nitrogen. 2. Only transfers problem from water stream to gas stream. Nitrogen may still need to be treated.
Advantages Eliminates all oxygen associated problems (explosion risk, fouling, corrosion). 2. Gas may be disposed as fuel gas or exported..
1.
Disadvantages
1. Gas may need compression for recovery. 2. Gas may have to be dried before it may be reused or exported. 3. May have less driving force for removing contaminants from water.
9.3.2.
9.3.2.1.
Performance variables
Hydrocarbon species Stripping is only suitable for the removal of volatile hydrocarbons which have an appreciable vapour pressure at the stripping conditions. The less volatile hydrocarbons will not be removed, including compounds such as the various glycols that may be present. Formic acid, acetic acid and methanol will not be effectively removed by gas stripping. Steam stripping which is discussed in section 9.4 may be used for the removal of less volatile components.
9.3.2.2.
Dispersed hydrocarbons Until recently, on the basis of previous investigations conducted by KSLA into the stripping of dispersed water from condensate (1982 - 1985, 3.02.2.d to h), it has been assumed that the removal of dispersed droplets from a liquid phase by gas stripping occurred by the dispersed hydrocarbons first dissolving into, and then being stripped from, the water phase.
PUXC 9-3-2
SIPM Droiliiiji M(oiic(i/.EP 93-I.?/.(.Rrv 1.1, Nov 1993. File iiomr = 903STRIP.DOC
9.3.2.3.Temperature
The performance of the stripping process will be affected by the operating temperature. The temperature influences a number of variables including: Mass transfer rate: Higher operating temperatures will improve the rate of mass transfer of hydrocarbons from the water to the gas phase. Vapour pressure: The vapour pressure of volatile hydrocarbons increases. Viscosity: Higher operating temperatures will lower the water viscosity, improving the mixing and mass transfer in the column. Saturation of stripping gas: The operating temperature may have an impact on the quantity of hydrocarbons that can be absorbed by the gas.
9 . 3 . 3 .
9.3.3.1.
Installation/Configuration
Process location
To minimise the size of the gas stripping equipment it is desirable to ensure the majority of dispersed hydrocarbons are removed from the water stream by upstream equipment. Thus gas stripping columns are usually located downstream of water treatment facilities designed for the removal of the majority of
9.3.4.
Design guidelines
The basic mass transfer theory governing the design of air and stream strippers is covered in detail in a range of standard chemical engineering textbooks. Additional information can be found in the references listed in the Bibliography. The physical parameters to be evaluated during the design stage are tower diameter, gas-to-water ratio, and packing type, size, depth and pressure drop. These parameters are interrelated. The number of transfer units, gas-to-water ratio and tower height influence removal efficiency and effluent quality. The gas-to-water ratio is dependent on the stripping factor and Henry's constant. Initial design calculations should be based on the compound to be stripped which has the highest concentration and the lowest Henry's constant. The packing size and the gas-to-water ratio affect the gas pressure drop. The practical limit for the gasto-water ratio is related to the pressure drop through the tower with the pressure drop rising as the gasto-water ratio increases. When using air, an air-to-water ratio of 15:l is considered to be low, ratios of 22:l to 30:l are better while a ratio of 50:l is considered high. Typical pressure drops are 0.8 to 4.2 cm of water column per meter of packing.
Pap2 9-3-4
SlPM Droiliir~ Mmriol. EP 93-131.5, Rev 1. I . Nov 1993, File ncrine = 903STRIP.DOC
The overhead stream from the stripper will consist of steam and hydrocarbons. This stream can be condensed, forming liquid water and hydrocarbon phases which can be separated. The hydrocarbon saturated water can be returned to the column and the separated hydrocarbons recycled to an appropriate part of the process or spiked into an export stream. Condensing of the overheads stream minimises the emissions from the stripping process apart from a relatively small vent flow of noncondensable gases. 9.4.1.1. Closed steam stripping
A closed steam stripping system is illustrated in Figure 9.4.1. A reboiler is used to evaporate a percentage of the product water stream which then rises against the down-coming water stream, stripping volatile hydrocarbons from the water.
The potential disadvantage of closed steam stripping is precipitation and fouling in the reboiler, particularly in the presence of saline waste waters . 9.4.1.2.
VaDour
Prehea ter
Condenser
Water reflux
Cooling water
Reboiler
H75117/9P
An open steam stripping system is similar to the closed steam svstem illustrated in Fiaure 9.4.1. However in place of a reboiler, dGect steam injection is used in the column. This eliminates the potential problems of boiler fouling and open steam stripping may be particularly attractive if a source of low grade steam is available.
+Treated water
9.4.2.
9.4.2.1.
Performance variables
Dispersed hydrocarbons Section 9.3.2.2 presents a range of arguments against the use of gas stripping for the removal of dispersed hydrocarbons. These arguments also apply to steam stripping, through the following factors will improve the removal of dispersed hydrocarbons in a steam stripping process. Higher operating temperatures will improve mass transfer rates. More of the heavier aliphatic compounds will be removed at the higher temperature.
9.4.3.
Installation/Configuration
9.4.4.
Design guidelines
See related information on gas stripping (section 9.3.4.).
Advantages
Disadvantages Energy cost. Potential scaling in column and/or reboiler for closed steam stripping. Cost of losing treated boiler water in open steam stripping systems.
3.
4.
5.
6.
vapour emissions are low. Can remove more non-volatile hydrocarbons by operating at higher temperatures or at sub atmospheric pressures. Economical if sources of waste heat are readily available. Improved mass transfer at elevated temperatures. Oxygen is excluded, minirnising organic and biological fouling and the need for expensive materials for corrosion resistance. Hydrocarbonsare recovered and returnedto the
P U ~ 9-4-2 C
SlPM DeoiI;il# Monuol. EP 93-1315. Rev 1.1. Nov 1993, File name = 904STfXM.DOC
9.5.2.
Aerobic processes
The following discussions present some of the common aerobic biological treatment systems. Aerobic systems produce a high quality effluent, but also produce a relatively large quantity of biomass in the form of sludge. Modifications to the aerobic process can minimise sludge production by encouraging the further metabolism of produced cell material by endogenous respiration. Up to 80% of the sludge can be oxidised but 20% is stable under aerobic treatment conditions and must be processed further. The aeration provided to enhance the aerobic treatment processes will have a stripping effect on the waste water. Volatile compounds such as aromatic hydrocarbons may be stripped from the water by the aeration rather than biologically degraded. The potential HSE implications of passing such contaminants into the atmosphere must be carefully considered.
Puxe 9-5-1
A range of modifications to this basic process can be considered such as contact stabilisation, extended aeration, step aeration and oxygen activated sludge. Each modification has characteristics which may suit different process requirements such as minimising complexity, minimising sludge production or maximising removal of contaminants. 9.5.2.2.
Fluidised beds
sludge process as the biomass is attached to the carrier particles and effectively has a long residence time in the reactor. This allows the biomass to be decomposed rather than just being produced as sludge.
Nutrients
Water
9.5.2.3.
Aerated lagoons An aerated lagoon is a basin, typically 2.5 to 5.0 m in depth covering a large area that is aerated by diffusion or surface agitation. In an aerobic lagoon the system must be well mixed to maintain aerated conditions throughout. In a facultative lagoon, only the surface of the lagoon is aerated and some solids settle on the bottom of the lagoon where they decompose through anaerobic processes.
9.5.2.4.
Trickling filters The trickling filter is an attached growth system where the waste water is passed (trickled) over microorganisms attached to a solid media. As the waste stream passes over the media the organics are oxidised by the attached micro-organisms. Historically the support media has been rock, however alternative media such as plastic and wood are now commonly used which can handle a higher water loading and a greater packing depth. Due to the short residence time, tricking filters cannot remove as much BOD as the activated sludge process, however, they are simpler to operate and can pre-treat high strength waste waters efficiently. However they may also be severely affected by rapid variations in the feed stream characteristics as there will be little or no dilution of the feed stream.
9.5.2.5.
Rotating biological contactors In rotating biological contactors the micro-organisms attach to a disc shaped support which rotates through a basin of waste water. The rotation of the discs contacts the biomass with the organic material in the waste water and then with the atmosphere above the water for oxygen adsorption.
P U ~9-5-2 C
SlPM D e o j h g Mrrriirol, EP 93-1315, Rev 1.1. Nov 1993. File ncrme = 905BIO.DOC
9.5.3.
Anaerobic processes
Anaerobic treatment converts soluble organic materials to methane, carbon dioxide and energy to support cell growth in the absence of gaseous oxygen. Anaerobic processes produce less sludge than aerobic processes with 80 to 95% of the biodegradable contaminants being converted to carbon dioxide and methane. Anaerobic process are typically used for highly contaminated waste waters containing at least 1,500 mg/l BOD and can handle a COD of 10,000 mg/l or higher. The anaerobic reaction consists of two stages. Conversion of soluble organic compounds to volatile fatty acids (mostly acetic acid) Digestion of the volatile fatty acids resulting in methane and carbon dioxide. The methane forming micro-organisms involved in the second stage are more sensitive to environmental conditions such as pH, nutrients and temperature than the acid forming micro-organisms in the first stage. The methane forming organisms also have a lower growth rate and will take longer to recover from inhibition or shock loading.
9.5.3.1.
Suspended systems
Suspended anaerobic conditions can be maintained in lagoons or vessels. Anaerobic lagoons can be used where close control of the process and a high degree of treatment is not required. The anaerobic contact process is illustrated in Figure 9.5.3. This process is similar to the activated sludge system combing a reactor and a settling tank with some sludge recycled. Figure 9.5.4 illustrates an up-flow blanket process where the biomass is suspended by the waste water flow. Solids concentration is controlled by periodic discharge of biomass while water clarity is maintained by setting the up-flow velocity lower than the settling velocity of the biomass blanket.
Reactor
ir
Underflow
H75117/12P
9.5.3.2.
Attached systems Because of the problems that may be experienced in clarifying suspended growth systems, attached growth systems are often utilised for treatment of wastes which are free from suspended solids. The micro-organisms attach to a fixed media, contacting the water stream. Up-flow and down-flow configurations can be used. Fluidised beds may also be used with the microorganisms attached to a fluidised media bed. This potentially allows both a higher loading rate and more surface area for growth of micro-organisms, resulting in a smaller reactor. A disadvantage is the energy required to fluidise the bed. An additional consideration is a need to be able to remove excess biomass from the system and to treat or recycle this excess.
_ M M M N
Gas collection
Sludge blanket
Feed
H75117/13P
Performance variables
Process environment
In order to support the growth of the micro-organisms the waste water must provide a suitable and stable process environment. Typical environmental conditions for biological systems are a pH of between 6 and 9, sufficient nutrients for growth, c 2:l variation in organics loading, < 125 mg/l suspended solids (TSS), 4 5 mg/l dispersed hydrocarbons, < 1 mg/l (typically) of heavy metals, and a temperature between 5 and 40C.Higher temperatures could possibly be accommodated with more thermophilic micro-organisms. Biological treatment systems have been effectively used for the treatment of a wide range of contaminants in relatively fresh water. However production waters from E & P operations are often very saline which can be a more difficult environment for the growth of suitable micro-organisms.
9.5.4.2.
Toxicity The micro-organisms present in a biological process are capable of adapting to a wide range of process conditions, allowing the processing of even relatively toxic contaminants. However, it is important to ensure that the process environment is maintained relatively constant. The environmental shocks from a rapid change of any parameter may result in a significant drop in biological activity until the system can adjust and recover. The system should thus be protected from any sudden changes in the process environment such as changes in temperature, pH, salinity or organic composition.
9.5.4.3.
Dispersed hydrocarbons The micro-organisms in a bioreactor live in the water phase and will not be able to effectively attack dispersed hydrocarbons. Where the biomass is attached to a substrate, dispersed hydrocarbons may result in fouling of the biomass support. It is recommended that the majority of dispersed hydrocarbons are removed upstream of the biological reactor.
9.5.5. 9.5.5.1.
Installation/Configuration
Process location Biological treatment systems should be located as a tertiary water treatment stage. This ensures the majority of dispersed hydrocarbons are removed upstream of the biological treatment systems and also helps ensure a more stable, consistent feed steam, protecting the system from surges or high loadings of contaminants.
9.5.5.2.
P q s 9-5-4
SIPM Deoiliitg Mnittrol, EP 93-1315. Rev 1.1, Nov 1993. File niiine = YO5BIO.DOC
Treatment process
Aerobic
Activated sludge Extended aeration Rotating biological contactor Trickling filter Aerated lagoon (aerobic) Aerated lagoon (facultative) Anaerobic Anaerobic reactor Anaerobic pond Facultative pond
Depth
(m)
'emoval (%)
BODS
Conditions
- 1.0
100 - 3,000
N.A. N.A.
0.5 - 3.0
50 - 500
500 - 3,000
50 - 750
4-9
2.5 - 5 2.5 - 5
3-10
50 - 250
80 - 95 Surface mixing
0.5- 30
N.A. 2.5
5 - 50
-5
7 - 50
1-2.5
c 25
1. Source: Waste water tre ment. Eckenfelder JI N.W., Patoc ka, J, Watkir 2. BOD Biological Oxygen Demand, F/M food to micro-organismratio, N.A. 1
iiiiiiir
= 9051110 DOC
~-
Puge 9-5.5
PUK" 9 - 5 6
SlPM Duoiliitl: Mniiiccil, EP 93-1315, Rev 1.1, Nov 1993. File nome = 905BIO.DOC
..
9.6.1.
9.6.2.
9.6.2.1.
Performance variables
Temperature and p H Activated carbon adsorption is normally conducted at temperatures lower than below 95C. As temperatures increase, the volatility of the compounds to be adsorbed increases, reducing their affinity for the absorption sites on the surfaces of the carbon. Adsorption of contaminants can also be enhanced or reduced by pH. In general a neutral or slightly acidic pH is most effective, however it is often found that acidic compounds are more effectively adsorbed in the presence of a low pH while bases are more effectively adsorbed in the presence of a high PH.
9.6.2.2.
Dispersed hydrocarbons and solids Dispersed hydrocarbons will tend to coat and block the pores of the activated carbon, reducing the capacity of the carbon bed. Solids will be filtered from the water by the carbon bed, however the system is not designed to act as a filter and the presence of solids will shorten the active life of the bed. Thus it is recommended that dispersed hydrocarbons and solids are removed upstream of activated cahon systems.
9.6.2.3.
Adsorption isotherm A liquid phase adsorption isotherm test is the basic preliminary evaluation tool to determine the ability of activated carbon to adsorb a given contaminant. The adsorption isotherm is determined through a batch test in which a fixed quantity of water sample is contacted with varying quantities of activated carbon. Results of an adsorption isotherm are usually expressed in terms of the capacity of the carbon for a given contaminant at a specified equilibrium concentration. A typical adsorption isotherm is illustrated in Figure 9.6.1. The isotherm curve will approach a straight line on a logarithmic plot and is mathematically described by the following expression known as the Freundlich equation (Eq. 9.6.1).
SIPM Droilink
Miiriiiiil.
Puge 9-6-1
-=kxC m where:
1 -
Eq. 9.6.1
m k C
= mass of contaminant adsorbed = mass of activated carbon = constant, related to the absorption of the contaminant = concentration of unadsorbed contaminant left in solution = sensitivity of the adsorption to contaminant concentration
Table 9.6.1 gives some typical Freundlich isotherm constants for single component adsorption from water. It can be seen that the water soluble alcohols and organic acids have a relatively low value of k and are thus poorly adsorbed compared to the aromatics and substituted aromatics.
Contaminant
Intercept k (mqlq)
Slope (lln)
Aniline Benzene sulphonic acid Benzoic acid Butanol Butyric acid Chlorobenzene Nitrobenzene Phenol Trinitrotoluene Toluene
1.
I
25 7 7 4.4 3 . 1 40 82 24 270 30
Source: Remove organics by activated carbon adsorption, Mark H Stenzel, Calgon Carbon Cop., Chemical Enqineering Progress, April 1993, pg 36 - 43
The adsorption isotherm can be used as a preliminary guide to determine whether a contaminant is likely to be successfully adsorbed by activated carbon, and provide an initial estimate of the quantity of carbon required. However, the isotherm does not provide sufficient information for detailed design. Dynamic testing or pilot trials are normally required to determine the practical performance of an activated carbon system when faced with complex mixtures of contaminants in production waters. This will evaluate factors such as the contact time required to achieve equilibrium and the shape of the contaminant breakthrough curve as the carbon bed becomes saturated.
9 . 6 . 3 .
1000
0.01
0.1
10
Toluene
- - Benzene
Figure 9.6.1 Single component activated carbon adsorption isotherms Illustrative only Not to be used for design
SIPM Droiliiiji
M~iiiiial. EP
Puxc 9-6-3
Puxe 9-6-4
9.7.2.
Co-current extraction
Conventional solvent extraction facilities use mixer/settlers or counter current contacting columns to achieve the required extraction. A more compact alternative is the use of a pseudo counter-current system as illustrated in Figure 9.7.1. This system consists of two or more co-current contact stages, each stage comprising a static mixer for co-current contacting and a hydrocyclone for separation of the produced phases. This process is essentially the same as the mixedsettler process, however the equipment is considerably more compact.
H75117110P
Coalescer /
Rich solvent
Lean solvent
Treated water
Key criteria determining the practicality of this system are the number of stages needed to achieve the required quality in the effluent water and the ability of the hydrocyclone to achieve a sufficiently high separation efficiency to remove the dispersed solvent from the water. This extraction system is undergoing pilot plant studies at KSLA. The estimated size and weight of such a system is compared with other processes for the removal of dissolved hydrocarbons in Appendix K.
riirrirr
= 907EXTRT.DOC
Puge 9-7-I
Pose 9-7-2
SlPM Deoilrnl: M U I I I ~ t ,P 93-1315, Rev 1.1. Nov 1993, File name = 907EXTRT DOC
10.1.
GENERAL
Due to the increased emphasis on environmental protection at both community and industry level, a range of new technologies are under development for the removal of contaminants from waste water streams. The following discussions present some of the promising technologies that are currently under development, either within Shell or by independent parties. Although these technologies are generally not yet commercially feasible or available at the present, they are presented to increase the general awareness of potential new developments which may in turn provide an impetus for their further development.
10.2.
OZONWULTRAVIOLET
Ozone/ultraviolet treatment is a chemical oxidation process. Ozone is generated by passing air or oxygen through a high voltage corona discharge. The ozone yield varies from 1 - 2% when using air to 3 - 5% when using oxygen. The ozone containing air or oxygen stream is then injected into the waste water st ream. By exposing the ozone containing water to ultraviolet light, oxygen radicals are generated that will chemically attack and break down the organic components of the water, producing carbon dioxide and water. The technology is suited to relatively low levels of contamination (less than 10 mg/l organics). It has the advantages of being relatively compact, achieving a reduction of organic contaminants to very low levels and does not produce any additional waste streams. This could potentially be considered as a tertiary treatment stage for the removal of relatively low levels of dissolved organic materials.
10.3.
10.4.
10.5.
PERVAPORATION
Pervaporation is a distillation process combined with a membrane separation. In a distillation, mixtures are separated by exploiting the different volatility of the components. Membranes separate mixtures by exploiting the different permeability of the components through the membrane. These separation processes can be combined in series by using a membrane at the vapour liquid interface. The composition of the vapour will thus be dependent on both the vapour-liquid equilibrium and the membrane permeability. Pervaporation can be used for the removal of dissolved volatile hydrocarbons from water. It can be thought of as vacuum distillation with the packed stripping column replaced by a membrane. A vacuum pump on the permeate side ensures a concentration gradient across the membrane, drawing both water
10.6.
. . .................,....
A.l.
Introduction
By definition, an emulsion is simply a dispersion of one immiscible liquid in another. When energy is input into such a dispersion it has two contrasting effects. Some of the energy will assist the emulsion, providing sufficient energy to the dispersed phase to support the dispersed droplets, overcoming their natural tendency to coalesce. However, at the same time, some of the energy input into the system will also increase the chances of dispersed droplets colliding and coalescing. For a given level of energy input into a system, there will be a maximum droplet size which is related to the dynamic equilibrium between the forces for dispersion and coalescence. For additional information on the concepts presented in this Appendix the user is referred to the following reference (Ref.l.08.1 .d); Flow induced coalescence in chemical dehydration, F. Meijs, W.J. van Beest, KSEPL report RKGR.0006.69, EP 40068, Jan 69
A.l.l
Mixing intensity
The mixing energy is defined as the work performed on a fluid per unit mass per unit time as expressed in equation A.l.
Eq. A.l
where:
= mixing intensity, the work performed on the fluid per unit mass per unit time (m*/s3) = pressure drop over a system (Pa) = retention time of the fluid in the system (seconds) = density of the continuous phase (kg/m3)
Ap
t pc
A.1.2
Eq. A.2
where:
,,, d
E
( r
It must be noted that this equation calculates the maximum stable droplet size that can be expected in an unstable emulsion that is not stabilised by the presence of emulsifying agents. In practice, many of the emulsions encountered in oil and gas processing are stabilised and thus the maximum droplet size will be smaller than that predicted by the Hinze equation. Also, the Hinze equation predicts the maximum droplet size, the averaae droplet size will be smaller.
Similarly, this relationship is only valid for liquid-liquid systems. The relationship expressed in equation A.2 will not be valid in a system containing free gas or where gas break-out may occur as the presence of gas will alter the manner in which energy is absorbed by the system.
A.1.3
P
4XPc x q
Eq. A.3
Re =
rrxpxD
Eq. A.4
Where:
v p
D q
= = = =
flowing velocity (m/s) dynamic viscosity (kg/(m.s)) piping inside diameter (m) flow rate (m3/s)
From the Reynolds number, the flow regime may be identified and one of the following equations can be used to calculate the mixing intensity. Laminar flow Fie < 1500)
E=
512 x p x q2
n xp,xD
or
E=
32 x p x v2 pxD2
Eq. A.5
32xfxq3
n3 xD7
or
E=-
fXV3
2xD
Eq. A.6
Where:
q f
p D
The friction factor f is the Moody-Weissbach friction factor and should not be confused with the Fanning friction factor. The friction factor may be read from a Moody diagram such as in the Shell Production
Poxe A-2
SIPM Deoiling Mor~iiol.EP 9.7-131.5, Hev I./. N(IV19Y3. Filv iwnir = YYAAI~INZ DOC
A.2.
These optimum mixing energy figures are difficult to apply to conventional deoiling equipment where it can be difficult to identify the location and length of time that a fluid is exposed to mixing energy in the form of pressure drop. However, pipelines provide a readily identifiable source of mixing intensity. The mixing intensities given above can be used to evaluate the possibility of using a pipeline to promote coalescence. The full results of these coalescence tests can be found in reference 1.08.1.d. and this reference also includes discussions on the application of these mixing intensities to pipeline systems in Oman and Nigeria.
100000
Q
al
10000
a l
1000
_ .
-0
.!i
2
a
100
I
0.01 0.1 1
10
100
1000
10000
100000
...x..
. 1 mN/m
5mN/m
-30mN/m
Figure A.l Relationship between maximum droplet size and mixing energy for a selection of hydrocarbon surface tensions
SlPM nroiliiiji
Miiiiiiiil,
Puge A-3
B.l.
Introduction
When sampling to measure a droplet size distribution, isokinetic sampling is required in the sample quill, however neutral conditions should exist in the majority of the sampling system. This method of sampling ensures that the droplet size distribution is not altered by the sampling procedure. In many cases, samples of dispersed hydrocarbons in water will be taken from relatively stable locations such as process piping where there is likely to be fairly neutral shear/coalescence behaviour. Thus the example calculation in this appendix actually demonstrates isoenergetic sampling, where the mixing intensity in the sampling system is kept equal to the mixing intensity of the process piping. In practice, the user should exercise their judgement in setting an acceptable mixing energy to maintain neutral behaviour in the sampling system. If the conditions at the point where the sample is taken are not neutral, the mixing energy in the sample system should be set to try and maintain neutral conditions. Some guidance on acceptable mixing energies can be found at the end of Appendix A. The following worked example is used to demonstrate the calculation of mixing intensities, the determination of the isoenergetic sampling rate and selection of the sampling quill size to achieve isokinetic sampling at the point where the sample enters the sampling system.
8.2.
p D p
= 790 m3/h = 0.2194 m3/s = 1025 kg/m3 = 0.3048 m internal diameter = 0.0006 Pa.s
From this information the mixing intensity being exerted on the fluid in the process line can be calculated using the equations presented in Appendix A. First the Reynolds number can be calculated from equation A.4.
R x 0.0006 x 0.3048
4 x 1025 x 0.2194
= 1,565,685
= 1,600,000
As Re > 3000, the flow is turbulent. From a Moody diagram, assuming that for clean steel the roughness is 0.02 mm, the friction factor f is 0.0124.
The mixing intensity E can now be determined from equation A.6.
E =
32xfxq
n3 xD
32 x 0.0124 x 0.2194
n3 x 0.3048
= 0.5530 m2/s3
E = 5530 cm2/s3
8.3.
w Needle valve
0
0
K K K K K K
= = = =
= =
1300 mm 1.3 m 3 x f (for each valve) 3xf 20 x f 12 x f (for each bend) 0.78 1.o
Losses after the last isolation valve will not affect the sample. The pressure loss within the sample container itself is assumed to be negligible.
2. Assume a samplina velocitv.
As the calculation is iterative a initial sampling velocity must be chosen. Try 1.O m/s as the initial guess. 3. Determine the samplina flow reaime in the samde line. The Reynolds number can be calculated from equation A.3. Re = pcxvxD
iJ
Re =
R e = 26.992 Re= 27,000 As Re z 3000, the flow in the sampling lines is turbulent.
Puge 8 - 2
SlPM Droiliirg Mnnictrl, EP 93-1315. Rev 1.1, Niiv 1993, File ntrme = 99BBISO.DOC
(fxDL)
fX(
+ (2 ~
1.3
15.8 x
+ (2 x 3) + 3 + 20 + (2 x 12)
KT = 0.027~(135.2785)+1.78 KT = 5.4325
6. Determine the pressure drop across the samplina svstem.
The following expression for pressure drop is taken from the Crane reference, equation 3-14. AP = 5 ~ 1 x 0 K T~ xpx? AP = 5 ~ 1 0 ~ -5 ~. 4 3 2 5 ~ 1 0 2 5 ~ 1 . 0 ~ AP = 0.0278 bar AP= 2784Pa 7. Determine the time sDent in the samplina svstem. Assume that the pressure drop is spread relatively evenly through the sampling system. This assumption is reasonable as there are no large point sources of pressure drop in the sampling system and the pressure drop through the piping dominates. Thus, the duration of the pressure drop is the time taken to traverse the sample piping.
t t
= -
1.3 1.0
= 1.3seconds
= 2.0893 mVs3
20.893 cm2/s3
Now this mixing energy is significantly higher than the mixing energy of 5530 cm2/s3in the main process
m
1025 x 0.65 x 0.0158 0.0006
Re =
Re = 17,545 As Re > 3000, the flow in the sampling lines is still turbulent.
From a Moody diagram, the friction factor f for a Reynolds number of 17,545 an internal diameter of 15.8 mm and a roughness of 0.02mm is 0.0292. 12. Determine the total flow resistances across the samdina svstem. Recalculate the total piping and fitting resistance KT.
5 ~ 1 ~0 5.7 ~3 0 1 ~ 1 0 2 5 ~ 0 . 6 5 ~
AP = 0.0124 bar AP = 1241 Pa 14. Determine the time spent in the samdina svstem. The duration of the pressure drop is the time taken to traverse the sample piping.
= -
1.3 0.65
= 2.0seconds
E
E
= 0.6054 m2/s3
= 6.054 cm2/s3
PURC8-4
SIPM Deoiliiig Mmiiwl, El' 93-1315, Rev 1.1. Nov 1993. File noinr = 99BBISO.DOC
The mixing intensity with a sampling velocity of 0.65 mls is very similar to the original mixing intensity in the pipeline. Thus 0.65 m/s is a suitable sampling velocity to achieve isoenergetic sampling.
B.4.
The overall volumetric sampling flow rate C is calculated by multiplying the sampling velocity and the cross sectional area of the sampling piping. q , =
vx-
xxD2 4
-3
4 , = 0.65~
)2
q , = 1 . 2 7 4 4 ~ 1 0 -m3/s ~
2. Determine velocitv in the main Drocess line
The fluid velocity in the process line being sampled is calculated from the volumetric flow rate and the internal diameter. vp = 4xa nxD2 4 x 0.21 94
vp =
n x 0. 30482
vp = 3.0 m3/s
D , =
4 x 1.2744 x 10-4 ~ ~ 3 . 0
D , = 7.3544 x 10-3 m
D , = 7.35 mm
Puxe B-5
The sample quill should have an internal diameter in the order of 7.4 mm. With the velocity in the main sampling lines of 0.65 m/s, isokinetic conditions will be achieved in the sample quill and isoenergetic conditions will be achieved in the remainder of the sampling system. The sample quill should be kept as short as possible to avoid adding mixing energy to the sample.
8.5.
The Reynolds number in the sample line can be calculated from equation A.3.
Re =
R e = 80,975 As Re > 3000, the flow in the sampling lines is turbulent. 3. Determine the friction factor. From a Moody diagram, the friction factor f for a Reynolds number of 80,975 in an internal diameter of 15.8 mm and a roughness of 0.02 mm is 0.0235. 4. Determine the total flow resistances across the samplina system. Recalculate the total piping and fitting resistance KT.
AP = 5 ~ 1 0 ~ -4 ~. 9 5 9 0 ~ 1 0 2 5 ~ 3 . 0 ~
AP = 0.2287 bar
A P = 22874Pa
6. Determine the time spent in the samplina svstem.
The duration of the pressure drop is the time taken to traverse the sample piping
t
= -
L
V
E U ~ E-6 C
1.3
3.0
= 0.433seconds
= 51.5383 m2/s3
E = 515.383 cm2/s3
8. Conclusions
It can be seen that the mixing intensity from iso-kinetic sampling is in the order of two magnitudes higher than the isoenergetic sampling (which in this case i s assumed to be neutral). This highlights the importance o f not using iso-kinetic conditions throughout the whole sampling f the dispersed phase system and trying to maintain neutral sampling when the size distribution o is to be determined.
P U ~8-8 C
SlPM Deoilirtx
Mtriirctil. EP
iltitiir
= 99BBISO.DOC
c.1
Test reference
Date
[l]
[2] [3] [4] [5] [6]
[7]
I
DEV H 17/181971
CONCAWE
~UNICHIM
I I
1971
I
Bestimmungvon Kohlenwasserstoffenmittels der lnfrarotintensitrits-Spektroskopie. (Determination of hydrocarbons by infrared intensity spectroscopy). Mineral oil in water by infrared spectrophotometry.
1972
I 1
I
U.S.A.
UK
Netherlands English
NBN
Dtltermination des hydrocarbures par spectrophotometrie Belgium infra-rouge. Bepaling van de koolwaterstoffendoor infrarood spectrofotometrie.
Petroleum hydrocarbons, total recoverable. (Spectrophotometric,infrared.) Method for the determination pf oil content. Effluents aqueux des raffineriesde petrol. Dosage des hydrocarburestotaux. Method of analysis for discharges from oil and gas production platforms. Methode danalyse pour les dtlversements des plateformes de production de gaz et dhuile. Determinationof oil and grease in water. Infrared spectrophotometricmethod Bepalingvan de olie-index met behulp van infraroodspektrometrie.(determination of the oil-index by infrared spectrometry) Standard test method for oil and grease and petroleum hydrocarbonsin water. Partition-infraredmethod (tentative) Hydrocarbons. Water Bepaling van het gehalte aan minerale olie met behulp van infrarood-spectrofotometrie (Water Determinationof mineral oil content by infrared spectrophotometry)
I lDutch
French and English English French English and French France
IItalian
[8] [9]
T90-203/79
Paris Commission Commission de Pans
AFNOR
____
Sweden
[lo]
[ll]
[12] [13] [14]
Swedish Standard
SS028145 ( 1979)
RlZA
Swedish
Netherlands Dutch
U.S.A U.S.A
English English
Netherlands Dutch
1989
[I51
1981
Germany
German
Source: Determinationof hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from
tiQ!.M
1.
2.
The informationcontained in this table has been reported as stated in the texts of the individual methods. No attempt has been made to amend it, even if it appears inconsistantin some cases. st: overall (total) standarddeviation so: single operator standard deviation
[3] CONCAWE
UNICHEM 1975
141
Minimum 1 determinability (ppm) 3 Sample volume (I) pH adjusted to Extractionsolvent Boiling point (C) Volume (ml) Extractionperformed: In By means of For Chrornatogpaphic adsorbent Column diameter (cm) Height of filling (cm) Quantity (9) Matter removed Wavelength (pn) Groups detected Calibration 3.42 3.50 CH2 CH2 original container
5
0.1
1
0.1
0.5
0.2
1
5
variable
5
___cc14 77 25
5
cc14 77
50
CCI4 77
cc14 77
50
cc14
77
50
loo+ 100
original container
original container shaking machine 100 strokeshin, amplitude 3.8cm 15 min Florisil added
original container
original container
shaking machine 100 mechanical strirrer strokeshin, amplitude 3.8cm 15 min 30 sec Florisil added
magnetic stirrer (4 cm hand or shaking machine 100 strokes long) per minute 15 rnin 15 min Florisil added Florisil
1
5 to 6
1 5
5
non-hydrocarbonpolar components aceous polar organic compounds 3.38 3.42 3.30 3.38 3.42 CH3 CH2 known oil or typical absorptivities (one normal, one for gasoline) CH CH3 CH2
most of the nonhydrocarbons 3.38 3.42 CH3 CH2 know oil or typical absortivities (one normal, one for gasoline) in the case of gasolines less accurate values are to be expected repeatabilitybetter than 10%
Precision
known oil or reference typical specific oil (37.5% iso-octane, absorptivities for CH, 37.5% cetane, 25% C H , CH, bands benzene) to the nearest ppm < 10 to 0.1 ppm > 10 to 1 ppm about *lo% for not suitable for highly known oil, &O% for aromatic products reference oil, such as tar oil and benzene, xylene, aromatic extract cumene essentially undetected about *lo%
reproducibility20%
Source: Determination of hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from
Ill@
c-2
iiifiiie
= 99CCIRED.DOC
Minimum C1 determinability(ppm) 1 Sample volume (I) pH adjusted to Extraction solvent Boiling point ("C) Volume (ml) Extractionperformed: In By means of For Chromatographic adsorbent Column diameter (cm) Height of filling (cm) Quantity (9) Matter removed separatoty funnel hand 2 min silica gel added c2 Freon 113 48 30+30+30
_-__
0.9 5 CClq
Swedish Standard SS028145 (1979) most components in mineral oil, some organic solvents, petroleum based part ot greases, petroleum based waxes 0.1 1.2 c2 CCI4
[lo]
77
50
77
50
original container
separatory funnel
*'2'3 1 10
5 other organic nonhydrocarbon matter separate detmn humic substance; high molecular aromatics; detergents, veg. fats, fatty oils, saponifiable grease, lactic fat, glycols, alcohols, ketones 3.38 3.42 CH3 CH2 known oil or reference oil (37.5% iso-octane, 37.5% cetane, 25% benzene) 10 to 0.1 ppm hydrocarbon mixture is used, i 30 40% in extreme cases. often better than i 2.5%
i 5 10% if
3.41 CH2
3.41 CH2
known oil or reference known oil oil (37.5% iso-octane, 37.5% cetane, 25% chloro-benzene) c 10 to 0.1 ppm 10-1OOto1 ppm loss of about half of some loss of volatile any gasoline present componentswill can be expected occur
Precision
!l.Q.ks
Source: Determination of hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from NEN 6673 (1981) to NEN 6675 (1989).
Test reference METHOD Matter revealed Minimum determinability (ppml Sample volume (I) pH adjusted to Extractionsolvent Boiling point (C) Volume (ml) Extraction performed In By means of For Chromatographic adsorbent Column diameter jcm) Height of filling (cm) Quantity (9) Matter removed
[ll]
r. i di .
r i 51
L._
0.8
2
Freon 113 148 30+30+30 Freon 113 Freon 113 77 20+20
i+15
30+30+30
25
separatory funnel hand or shaking machine 100 strokes/min. 2 min silica gel added
original container
Ioriginal container
or three dimensional
i min
lrisil added
l2
I
3 complex aromatic compounds, chlorine sulphur-nitrogenhydrocarbon derivatives; Freon insoluble material from heavier residue! 3.41
dar components
42
3.41
Precision
d !Q .m ! .
1.
{drocarbons in aqueous effluents by infrared analysis, Concawe Report 0.1/84, March 1984. NEN method upgraded from 1 NEN 6675 (1989).
typical specific typical absorptivities absorptivities for CH, for CH, CH?, C H , C H , CH, bands bands or known oil or squalane or isooctane/cetane/benzen e 4 0 to 0.1 ppm >10tolppm less suitable for average recovery highly aromatic 97.2%; gasoline may products (tar oil and not be measured aromatic extract) (ratio of absorption at 3.30pm:3.42pm > 0.23) oil: (37.5% isooctane, 37.5% cetane, 25% benzene)
2.
The information contained in this table has been reported as stated in the texts of the individual methods. No attempt has been made to amend it, even if it appears inconsistant in some cases. st: overall (total) standard deviation so: single operator standard deviation
Pu,qe c-4
SlPM Dending Moniid. LP 93-1.jI5. Hrv 1.1. Nov 199.3. File nome = Y9CCIRED.DOC
D.l
D.1.2.
Monitors tested
The names, basis of operation and suppliers of the oil-in-water monitors tested in the Phase I trials are listed in Table D.l. It should be noted that due to installation problems no effective results were obtained for the Teledyne unit.
Oil-in-water monitor Bristol Babcock OCD-30 Facet Mark Vlll Bilge Alarm Horiba OCMA-25 Monitek Micro-Pure MPS-D Pure Alert Oili-S Type 300 Schlurnberger Oilcon EJB51 Teledyne 661R
Basis of operation Infraredlight scattering Infraredlight scattering Infrared absorption with solvent extraction Ultrasonic Direct infrared absorption Infrared light scattering Ultraviolet direct absorption
Supplier Bristol Babcock Ltd Facet Industrial UK Ltd Horiba InstrumentsLtd Monitek Technologies Inc OPTEC-InternationalLtd SchlurnbergerIndustries Ltd Teledyne Analytical Instruments Ltd
D.1.3.
Variables investigated
The variables listed in Table D.2 were investigated during the Stage I trials. As the Phase I oil-in-water monitor trials were integrated with other test work, the scope to freely adjust these variables or to repeat tests was limited.
Table D.2 Variables investigated for oil-in-water monitor trials Phase I
Variable Oil concentration Oil droplet size Free gas content Process chemical content Aromatic hydrocarbon content Oil density Solids content
6 to 30 prn.
Method I range 20-75 rngA while keeping droplet size relatively constant. Flotation or cyclone effluent, free gas not measured or controlled. Flotation aid, corrosion and scale inhibitor, demulsifier.
n g l toluene. Addition of 20 r
Normal oil/fuel oil.
14 and 60 mgA of sand, 300pm average particle size.
All monitors were found to be insensitive to the level of dissolved aromatic hydrocarbons.
D.2 D.2.1.
- Phase II
A second series of trials with oil-in-water monitors was conducted over the period of November 1990 to March 1991. The following report was issued and is available from SIPM EPD/421 on request.
Oil in water trials conducted at the Orkney Water Test Centre, November 1990 to March 1991, Tullock, S.J., Oct 1991, EP-No.91-2151
D.2.2.
Monitors tested
The names, basis of operation and suppliers of the oil-in-water monitors tested in the Phase I I trials are listed in Table D.3. The OCD-37, Monitek, Oili-S and Oilcon monitors were improved versions of the monitors tested in Phase I.
Oil-in-water monitor Fluoritest-S OCD-37 Monitek MPS-D Pure Alert Oilcon effluent monitor Oili-S Mark 1000 C Turner Model 10
I
Basis of operation Ultravioletfluorescence Infrared light scattering Ultrasonic Light scattering Direct infrared absorption Ultravioletfluorescence
I
Supplier Puskds Tivadar cooperative Rivertrace Engineering Ltd Monitek Technologies Inc VAF Instruments OPTEC-International Ltd Turner Designs
POKCD-2
SIPM Droiliiix Miriiiral. EP 93-1315, Rev 1.1. Niiv 1993, File nomc = 99DDMONS.DOC
Variables investigated
The variables listed in Table D.4 were investigated during the Stage II trials.
Table D.4 Variables investigated for oil-in-water monitor trials Phase I 1 Variable Oil concentration Oil droplet size Oil type Water temperature Free gas content Process chemical content Ambient temperature Long term operation Scaling Soluble hydrocarboncontent Oil density Solids content
Method I range 20-100 mg/l. 10,17.5,25 and 50 Mm. 36" Flotta crude, 21" fuel oil, 56" condensate.
7.5,25, 40 and 70C.
Gas breakout in hydrocyclone effluent. Corrosion inhibitor, demulsifier. 15 and 25C. Over a period of 21 days. CaCI2 and Na2C03 injection. Addition toluene and acetic acid. Normal oilMuel oil. Diatomaceous earth, 50pm average particle size.
D.2.4.
Summary of results
In general, in the Phase II trials it was again concluded that none of the monitors could be recommended as a reliable and accurate method to replace the manual sampling and analysis methods currently used for effluent water analysis. Due to the number of monitors and variables investigated it is not practical to summarise the results in this manual. Most of variables tested had some effect on the monitors, though the magnitude of the effect varied for each monitor. Users requiring detailed information are referred to the original report. However the following significant points were noted from the trials. The performance of the units was significantly better than the Phase I trials. Most of the instruments measured oil concentrations to *lo%.
Most of the monitors tended to over estimate the hydrocarbon content when using 56 "API condensate, even after recalibration.
None of the monitors tested detected the presence of dissolved hydrocarbons (toluene and acetic acid). (The Fluoritest-S and Oili-S monitors were not operational for this test.) The Performance of the monitors deteriorated in the presence of free gas and solids. However not all monitors were operational for this test.
~I<III= I~
99flflMONS.flOC
Page 0 - 3
D.3
IR light scattering
E.l.
E.1.2.
Analysers tested
The names, basis of operation and required sample conditions of the particle size monitors tested is listed in Table E.l.
Table E.l Particle size analysers tested at OWTC Particle size analyser Coulter LS130 Coulter Multisizer Galai CIS-1002 Lasentec Partec 250 Malvem Mastersizer Basis of operation Laser diffraction Aperture counting Laser time of transition Fonvard scattering Sample Condition Batch, sample depressurised. Batch, sample depressurised, sample dilution may be required. Continuous, at process conditions up to 12 barg. Continuous, analysis probe can be inserted directly into the process piping (up to 10 barg). Batch or continuous, sample depressurised.
E.1.3.
Variables investigated
The variables listed in Table E.2 were investigated in the OWTC particle size analyser trials.
Variable Hydrocarbondroplet size Hydrocarbondroplet concentration Hydrocarbon type Free gas content Solids content
range Method I
5 to 50 pm
20 to 100 mgA
E.1.4.
Summary of results
All of the analysers except one were found to perform well. Users requiring detailed information are referred to the original report.
Of the analysers tested, the Galai appeared to be particularly promising as it supported the following functions:
SlPM Deoilirig Moriiinl. EP 93-121.(, R n 1.1. NIIV 199.1. File iiww = 99fiLSIZLDOC
Puxe E-1
The instrument is readily portable and will give instant results on site.
In view of the promising results from the OWTC trials and the potential advantages of the instrument, KSLA have conducted an investigation to compare the performance of the Galai with the KSLA method of microphotographyand image analysis. The results of this comparison are summarised in the following section.
E.2. E.2.1.
If there are too few dispersed droplets the Galai may not be able to give a result. This may be a problem at low hydrocarbon concentrations or with a relatively small number of large droplets.
If there are too many droplets, interference with the laser may result in incorrect results. There is some doubt over the ability of the instrument to clearly differentiate between liquid droplets and solid particles. The original orientation of the sampling cell allowed bubbles to accumulate and coalesce until a single large bubble detached and passed through the measuring system. This was corrected by altering the orientation of the sampling cell.
E.2.2.
Conclusions
Although under most conditions the Galai size analyser was found to give a droplet size distribution comparable to the KSLA size analysis technique, there appear to be certain operating conditions where the results from the Galai are not reliable. At this stage, further work is required to clearly define the operating envelope in which the user would be confident of obtaining representative results from the Galai, particularly with respect to the sampling velocity and droplet population density. Until the operating envelope is more clearly defined the Galai cannot be recommended as a suitable method for measurement of droplet size distributions in the field. Vortoil are developing a version of the Galai (the D-100) which with new software will be able to measure both droplet size distribution and to infer the concentration of dispersed hydrocarbons. The unit is Ex qualified for use in hydrocarbon areas and may have significant promise as a trouble-shooting diagnostic tool for water treatment equipment. The potential advantages of the Galai or Vortoil instruments for on-site measurement of droplet size distributions at operating conditions means that further test work is recommended. SlPM EPD/42 should be contacted to determine the current status of development .
Puxe E-2
SlPM Duoiliiil: Mwiud, EP 93-1315, Rev 1.1. Nriv 1993, File noine = 99EESIZE.DOC
F.l.
Derivation
Provided a density difference exists between the hydrocarbon phase and the water phase, a dispersed hydrocarbon droplet will experience a buoyant force as expressed by equation F.l.
Eq. F.l buoyant force (N) gravitational acceleration, (m/s*) dispersed droplet size (m) density of the continuous water phase (kg/m3) = density of the dispersed hydrocarbon phase (kg/m3)
where:
F , g d pw ph
= = = =
In most cases the hydrocarbon density will be lower than that of the water phase and the dispersed droplet will experience a positive buoyant force causing the droplet to rise upwards.
As the droplet rises through the continuous phase, the buoyant force will be opposed by a drag force on the droplet. The drag force is expressed by equation F.2
Eq. F.2 drag force (N) drag coefficient dispersed droplet size (m) density of the continuous water phase (kg/m3) droplet velocity relative to the continuous phase (m/s)
where:
= = = pw = v =
Fd
When the buoyant forces and drag forces are in balance the droplet will rise with a constant terminal velocity vT. For a dilute dispersion of small hydrocarbon droplets in a water phase the Reynolds number is generally less than 10 and the following approximation for the drag coefficient may be used. 24 =Re
cd
Eq. F.3
where:
Re =
p
pwxvxd
Equating the equations for the buoyant and drag forces (F.l and F.2) and substituting the approximation for the drag coefficient (F.3) and Reynolds number results in the derivation of Stokes Law, as expressed by equation F.4.
SIPM DeoiliiiK Mmrtal. EP 93-1315, Rev 1.1. Nov 1993. File iiiisir = 99FFSTOX.DOC
Puxe F-I
F.2.2
Gravitational acceleration
The acceleration force due to gravity is constant at 9.81 m/s*. However hydrocyclones and centrifuges operate by imposing a centrifugal acceleration on the system. This centrifugal acceleration can be several orders of magnitude higher than gravitational acceleration and will increase the terminal rising velocity of a droplet proportionally.
F.2.3
Viscosity
The terminal rising velocity is inversely proportional to the continuous phase viscosity. Lowering the viscosity of the continuous phase (e.g. by raising the temperature) will increase the rising velocity.
F.2.4
Density difference
There must be a density difference between the two phases for the hydrocarbon droplet to experience a buoyant force. The larger the density difference, the larger the terminal velocity. In most cases the hydrocarbon phase will be less dense than the water phase, leading to a rising hydrocarbon droplet. The density of each phase will change with temperature. The effect of temperature on the terminal rising velocity of a hydrocarbon droplets is discussed further in Section F.3.
F.3.
J , as the temperature All three emulsions exhibit a decrease in the continuous water phase viscosity I rises. The defining characteristic for each type of emulsion is thus the variation of the density difference between the phases with temperature.
Type I emulsions have a continual widening of the density difference with temperature. Thus as shown in Figure F.4 the terminal velocity increases with increasing temperature. Type II emulsions have a narrowing of the density difference between the phases as the temperature rises. Thus as illustrated in Figure F.5 the terminal velocity will reach a maximum value at an optimum combination of viscosity and density difference and then will start to fall. Further increases in temperature beyond the maximum terminal velocity will be detrimental to the separation. In Type I l l emulsions, different rates of density variation with temperature result in a crossing of the density-temperature curves for the two phases. At the temperature where the curves cross, there will be no density difference and the droplet will be neutrally buoyant. As the temperature increases further the system will invert with the hydrocarbon droplets becoming denser than the water phase and falling rather than rising through the continuous water phase. This behaviour has been observed numerous times in heavy oil fields. This behaviour highlights the influence of temperature on Stokes law. Examination of Stokes law
POKCF-2
SIPM Deoiliiih. Maiirtrtl. EP 9.1-1315, KKV 1.1, N:IV 1993, File nrimr = 99FFSTOK.DOC
Appendix I; - Stokes h w
illustrates that for a given droplet size and gravitation force the terminal velocity is only proportional to the density difference and the continuous phase viscosity Le. vt a
(Pw -PtJ
CI
This term, formed by the density differential divided by the viscosity is known as Stokes parameter.
e
1L
x c .-
a 5
J
0 50
E
Temperature "C
100 150
H7$a7xmY
W 0 .
i71/(
50
Temperature "C
100
150
Pw
'8
c
_ I
i?
W
50
Temperature "C
100
150
g +
I
50
Temperature "C
100
150
I o
50
Temperature "C
100
I5O
I
Figure F.6 Type 111 emulsion: Terminal velocity vs temperature
HIS P INTENTIONALLY LE
NK
Puxe F-4
SlPM Deniliiil: Monucil, EP 93-1315, Rev 1.1. Nov 1993. File ncrme = 99FFSTOK.DOC
G.1.
Introduction
The equipment presented in these discussions represents a range of coalescers known to SlPM through trials, installations or vendor contact. Presentation in this manual does not suggest a particular preference for any particular equipment or supplier and specific equipment brands should be considered as illustrative of the various generic classes of coalescer.
A number of these coalescer designs have been tested at the OWTC. The results of the tests are contained in the report;
Testing of coalescing devices to enhance the performance of hydrocyclones at Orkney Water Test Centre, Webster, J.D., March 1992, EP-No.92-0942. Some of the results are briefly summarised in the following discussions and in Figures G.7 to G.9.
G.2. G.2.1
Eventually the droplets grow to such a size that viscous drag forces acting on the droplet (as a result of the continuous fluid flow through the coalescer) will dislodge the coalesced droplet from the coalescing media.
G.2.2
Packaging
A number of coalescer elements are typically installed on a mounting sheet as illustrated in Figure G.l
Water outlet
U 4 II
Oil outlet
I/ I
G.2.3
Performance
The Knitmesh Dusec cartridge has been tested at the OWTC and found to effectively coalesce condensate and medium density crude oil. Results were not as favourable for heavy crude oil (see Figures G.7 to G.9). The Dusec cartridge has also been successfully tested for the removal of water from condensate (Ref.2.14.2.c). Similar cartridge type coalescer elements are available from a number of suppliers such as Peco, Alan Cobham, Plenty and Warner Lewis. These cartridges are manufactured from a range of materials such as fibreglass, polypropylene and paper. A number of these cartridges have undergone laboratory trials to measure their performance in the removal of dispersed water from condensate (Ref.2.14.2.c and 2.14.2 .d) .
The Knitmesh DC is a coalescing mesh composed of dissimilar materials, typically a metal and a plastic material. The junctions formed between these materials are believed to improve the coalescing performance of the mesh. The DC mesh is designed for use as a primary coalescing material for relatively large dispersed droplets and would be typically installed vertically across a horizontal separator. The Knitmesh DC coalescing mesh has been used successfully at the Shell Stanlow and Pernis refineries. The Knitmesh DC mesh is also used as the outer layer on the previously discussed Knitmesh Dusec coalescing cartridge.
G.4. G.4.1
tivdrocvclone coalescer
Description
In addition to the normal use of hydrocyclones for hydrocarbon/water separation, hydrocyclones may also be used as coalescers. In coalescing mode the centrifugal forces generated in the hydrocyclone concentrate hydrocarbons at the core of the cyclone, where if conditions are favourable they have a higher probability of coalescence (due to the higher concentration of droplets). In coalescing mode the hydrocarbon reject port is blanked off and the coalesced hydrocarbons leave with the water stream from the underflow of the cyclone. In coalescing mode the cyclone is operated at throughput lower than the normal separation capacity. In the case of the Vortoil F liner design, Vortoil recommend that in coalescing mode the cyclone is operated at 6.6 mVh, compared to the nominal 8.1 m3/h capacity for normal separation duties. A recycle stream can be used to improve the coalescing performance of the hydrocyclone.
G.4.2
Packaging
Packaging is similar to the normal hydrocyclone systems discussed in section 8.9. The normal hydrocarbon reject port is blocked off and a recycle stream may be used to aid coalescence. The coalesced stream would typically be used as feed to a downstream set of separation hydrocyclones.
G.4.3
Performance
A Vortoil hydrocyclone operating in coalescing mode has been tested at the OWTC with generally favourable results with good coalescence of droplets smaller than 20 pm. For condensate and light oils the coalescing efficiency improved significantly with a 50% recycle. However for heavy oils the performance deteriorated with a recycle (see Figures G.7 to G.9).
PURCC-2
SIPM Dcoiliiix Mctr~irrrl.EP 93-1315, Rev 1.1. Nov 1993. File noinr = 99GGCOAL.DOC
G.5.2
Packaging
The SP pack is packaged box enclosing the serpentine flow path and is designed to be installed internally in tanks or vessels. The internals of the SP Pack are generally constructed from PVC and fibreglass.
G.5.3
Performance
Testing at the OWTC indicated that for low oil concentrations (<400 mg/l) the SP Pack had a coalescing efficiency only in the order of 10% for droplets smaller than 40 Vm (see Figures G.7 to G.9). Performance was better for higher hydrocarbon concentrations in the order of 800 mg/l. This performance is unlikely to make a significant improvement to most downstream deoiling separation equipment, with the exception of gravity based separators such as skimming tanks. The SP Pack design has been used successfully in the USA, installed on the inlet feed to a skimming tank for the coalescing of relatively large hydrocarbon droplets (Ref.2.14.2.b).
G.6. G.6.1
G.6.2
Packaging
The Spiralsep unit is an in-line coalescer and is installed as normal piping. A minimum liquid velocity in the order of 4.3 m/s is required through the unit to promote coalescence.
G.6.3
Performance
Testing at the OWTC indicated that for low oil concentrations (<400 mg/l) the Spiralsep had a relatively poor coalescing efficiency for droplets smaller than 40 Vm (see Figures G.7 to G.9). Performance was better for hydrocarbon concentrations in the order of 800 mg/l.
G.7. G.7.1
G.7.2
Packaging
The Mellapak may be manufactured to any reasonable diameter or shape.
G.7.3
Performance
Testing at the OWTC indicated that the Mellapak structured packing only exhibited significant coalescing properties with hydrocarbon concentrations in the order of 800 mg/l (see Figures G.7 to G.9).
Backwash
Coarse Lipophilic
Coarse Garnet
Figure G.2 The advantage of the filterlcoalescer designs would Natco VFX filterlcoalescer appear to be the longer filtration cycle times compared to filtration only processes. This is because the length of the filtration.cycle will be governed by the solids loading rather than the hydrocarbon loading. However there are several potential disadvantages with the filter/coalescer design. The best coalescing performance would be expected with relatively high oil contents (>lo0 mg/l). However, this conflicts with deep bed media filtration experience which suggests fouling of the media bed can be a significant problem with high hydrocarbon concentrations or heavy oils. It is not known whether the media coalescer would be subject to same problems with fouling and mudballing of the media. In addition, due to the upflow configuration, the flux rate through the bed will be limited by the need to avoid bed fluidisation. The normal filtration/coalescing fluxes are in the order of 18 to 20 (m3/h)/m2. There are no known installations of the Natco VFX or the Degremont Colexer filter/coalescer within the Shell group.
G.9.
out
Backwash
Operating mode
Puge G-4
SlPM DrorlrriC: Mcriiutrl. EP 93-1315. Rev I I. Nov 1993, File ncrmr = 99GGCOAL.DOC
Upflow
Oil
Downflow
As with the upflow filterkoalescers, the advantage of the filter/coalescer designs would appear to be the longer filtration cycle times compared to filtration only processes as the length of the filtration cycle will be governed by the solids loading rather than the hydrocarbon loading. As the filterkoalescer is designed to carry hydrocarbons through the filter bed and is operating in a downflow configuration, the flux rate through the filter is claimed to be high, in the order of 2 to 3 times higher than a conventional downflow filter.
downstream separation
To
However, as with the upflow filterkoalescers the best coalescing performance can would be expected with relatively high oil contents (3.100 mg/l). However, this conflicts with deep bed media filtration experience which suggests fouling of the media bed can be a significant problem with high hydrocarbon concentrations or heavy oils. It is not known whether the media coalescer would be subject to same problems with fouling and mudballing of the media. There are no known installations of the Skimovex filterkoalescer within the Shell group.
G.11.
O l i
Packi
Deoiled water
Treated
water
Oily m
,Y)26110P
YTLOmIP
Figure G.6 Elf Anvar downflow filter/coalescer with integral gravity separation compartment
The resin bed thickness is in the order of 300 mm with an allowable fluid flux of 12.5 to 20.0 (m3/h)/m2. The inlet stream would typically contain 10-100 mg/l of dispersed hydrocarbons with a claimed outlet hydrocarbon concentration below 1 mg/l. Most applications to date have been in the deoiling of relatively
~~~
SlPM D r o i l t n ~ Mmiiitl. EP 93-1315, Rev 1.1, NOV199.7. Tilt, ii(tiiie = 99C;GCOAL DOC
Pqe
G-5
G.12.
Plate interceptors
Plate interceptors are widely used for the coalescence and separation of dispersed hydrocarbons from water. The close spacing of the plates (20-40mm) ensures that the flow regime between the plates is laminar, allowing small hydrocarbon droplets which would normally be dominated by turbulence to rise relatively unhindered. The proximity of the plates ensures that a hydrocarbon droplet only has to rise a short distance before it intercepts the underside of a plate. The concentration of hydrocarbon droplets on the underside of the plate promotes coalescence of the hydrocarbon droplets. Plate pack interceptors are generally packaged to achieve both coalescence and separation. They are discussed in detail in Section 8.8.
G.13.
Natco Performax
Natco Performax is a coalescing matrix designed to be fitted across horizontal separation vessels. The matrix acts in a similar manner to a plate pack interceptor, reducing both turbulence and the rising distance to improve phase separation. The Performax matrix may either be installed as original equipment to minimise the size of the separation vessel, or may be fitted to most separators to improve throughput or separation performance. The matrix has also been used to minimise the effect of wave motion in separators located on floating production vessels. The Performax matrix has been successfully fitted to Shell Expro locations (Lowestoft and Leman).
P U ~ G-6 C
SlPM Deoilircl: Mnriiccrl. EP 93-1315. Rev 1.1, Nov 1993. File rcctnir = 99Cc'COAL.DOC
Droplets c 10 pm
Droplets c 20 pm
I I Droplets < 40 pm
Figure G.7 Comparative performance of coalescers 200 mgh of 56" API condensate (Dispersed in sea water at 55"C, 20 pm median droplet size)
60
40
20
'
Q m
C .-
-40
-60
. -
. .
. .
-80
-1 00
Droplets < 10 pm
Droplets < 20 pm
I I Droplets < 4 0 4
Figure G.8 Comparative performance of coalescers 200 mg/l of 37" API crude oil (Dispersed in sea water at 55"C, 20 pin median droplet size)
-1 00
Droplets < 20 pm
Figure G.9 Comparative performance of coalescers 400 mgA of 21" API heavy oil (Dispersed in sea water at 5 5 T , 35 pm median droplet size)
P U ~ G-8 C
SIPM Deoiliitx Miiitwl, EP 93-1.715. Re\, 1. I , Nov 1993. File mmr = 99GGCOAL.DOC
H.l.
Introduction
The following equations can be used for the preliminary sizing or performance evaluation of plate pack interceptors. For detailed engineering sizing the user is referred to appropriate equipment vendors or the Shell documents referenced at the end of this Appendix.
H.2.
Revnolds number
The Reynolds number through a plate pack should be 800 or lower for flat plates or for corrugated plates when the flow is in the direction of the corrugations. The Reynolds number should be less than 400 if the flow direction is across corrugated plates.
It should be noted that the Reynolds number does not constrain the capacity of the plate pack, only the frontal area of the plate pack. For example, a pack with a Reynolds number restricted to 400 will require a wide frontal area, but due to the low velocity through the pack, can achieve the required droplet separation in a short pack length.
A plate pack with an allowable Reynolds number of 800 can have a smaller frontal area, but due to the higher velocity through the pack will require a longer pack length for separation. The actual flow capacity, separation ability and plate pack volume of each pack will be the same. Just the aspect ratio between the pack frontal area and pack length will be different. This is demonstrated in section H.5. The Reynolds number for flow between two plates can be calculated from the following equation. Re = Where:
pw = water density (kg/m3) p v
= dynamic viscosity (poise or kg/(m.s)) = water velocity (m/s)
pw x v x 4 x R H
Eq. H.l
R ,
The hydraulic radius RH is strictly defined as: RH = area of stream cross section wetted perimeter
Eq. H.2
For a rectangular flow channel, the hydraulic radius is: RH = Where: wxx 2 x (w + x ) Eq. H.3
x W
However, for most cases, W >> x, thus equation H.3 can be simplified to: RH = 2 Substituting H . 4 into H.l Re =
pwx v x 2 x x
CI
X
Eq. H.4
Eq. H.5
Now, the velocity v through the plates is equal to the overall volumetric throughput divided by the plate pack area A. Therefore,
PXA
Eq. H.6
= volumetric flow through the whole plate pack (m3/s) = plate pack cross sectional area (m*), = Width of pack (W) x Height of pack (H)
H.3.
Eq. H.7
L
VT
= inclination of plate pack (horizontal = O", vertical = 90') = plate length in the direction of flow (m)
= terminal rising velocity of hydrocarbon droplet (m/s) (Eq. F.4, Appendix F) = 0.9 (Factor to allow for turbulence in initial sections of plate pack)
Equations H.6 and H.7 may be used either to calculate the required size of plate pack to achieve a specified separation duty or to determine the potential separation performance of an existing or standard sized plate pack.
H.4.
Example
Determine the dimensions of a plate pack required to separate hydrocarbon droplets of a given size. For example, determine the size of plate pack required to separate 60 pm hydrocarbon droplets from a waste water stream of 80 mVh. Assume a rectangular plate pack, a water density of 1000 kg/m3, hydrocarbon density of 900 kg/m3, water viscosity of 0.8 cP.
1.
Assuming the water stream is relatively clean, choose a plate spacing of 20 mm and a plate inclination of 45'. Determine the droplet rising velocity from Stokes law as defined by equation F.4 in Appendix F.
2.
.. .. ..
3 .
VT
x (1000 - 900)
18 x(0.8 x ~ O - ~ )
-4
vT = 2 . 4 5 ~ 10
m/s
vT = 0.245 mm/s
Determine the allowable cross sectional flow area of the plate pack to achieve a Reynolds number of 800, using equation H.6. Re = pwxqx2xx PXA
P q e H-2
SIPM Droiliiix
Mrrriiciil. EP
..
Eq. H.8
..
4.
= 1.39 m2
To achieve the required cross-sectional area assume a plate pack of dimensions 1.2 m wide, 1.2 m high. From equation H.7 determine the required length of the plate pack.
LxA= qxx
COS( 0) X V T X F
..
..
Lx1.2x1.2=
($&) x 20 x 1 0 - ~
cos(45")x2.45x10-4 xo.9
Eq. H.9
L = 1.98m
Therefore, a plate pack of dimensions 2.0 m x 1.2 m x 1.2 m (LxWxH), 20 mm plate spacing and 45" inclination will achieve the desired separation.
H.5.
..
..
400 =
Eq. H.10
= 2.78 m2
Assume to satisfy this area criteria, the width and height of the plate pack are 1.4m and 2.0m respectively. Substituting into equation H.9 gives;
..
..
Lx2.Ox1.4 = L = 1.02m
( 3600 )
cos(450) x 2.45 x lo4 xo.9
Eq. H . l l
Therefore, a plate pack of dimensions 1.O m x 2.0 m x 1.4 m (LxWxH), 20 mm plate spacing and 45" inclination will achieve the desired separation. Thus, the effect of the lower Reynolds number is to require a larger plate pack cross-sectional area. However, because the velocity through the plates is lower, the length of the plates can be less to achieve the droplet separation. The volume of both plate packs is identical; Re = 800, volume = 2.0 m x 1.2 m x 1.2 m = 2.8m3 Re = 400, volume = 1.O m x 2.0 m x 1.4 m = 2.8m3 Naturally, some judgement must be applied when setting the relative dimensions of a plate pack. Very short plate lengths will not be as efficient as longer plates as the disturbances from the entrance to the plate pack will affect a larger percentage of the plate length. In most cases, mechanical, process and vessel layout requirements will restrict the allowable practical dimensions of a plate pack.
Puxe H-3
PUXCH-4
iiciine
= 99tfI!PlAT.DOC
1.1
Introduction
The concepts and discussions presented in this appendix are designed to introduce the user to some of the methods of characterising and predicting the performance of hydrocyclones. For more detailed information on these concepts the user is referred to the following references.
[I]
[2] [3] [4] [5]
Comparative testing of new generation deoiling hydrocyclones, OWTC Report, Aug 1992, EP 92-1900. Hydrocyclones, Svarovsky, L., Holt, Rinehart and Winston, London, 1984 Correlation of separation results from light dispersion hydrocyclones, Colman, D.A., Thew, M.T., Chem Eng Res Des, Vol. 61, July 1983, Ref.2.05.l.g. The Hydrocyclone, Bradley, D., Pergamon press, London, 1965 The design of hydrocyclones, Rieterna K., KSLA report number 26986A, Oct 1956
1.2
1 , then d=d5,
nd,out
Eq. 1.1
Another commonly used cut size is ,, d , representing the hydrocarbon droplet size with a 75% chance of being removed from the water stream.
1.3
1.3.1
Eq. 1.2 The Reynolds number Rei is defined at the hydrocyclone inlet;
Eq. 1.3
This model was originally developed for narrow angle solid/liquid hydrocyclones. It should be noted that this model does not consider potentially important variables such as radial fluid flow, hindered settling effects, droplet coalescence or the effect of turbulence.
1.3.2
[
/
Pc
\ 0.5
(Rei)1'375x Ap]
Eq. 1.4
As for the equilibrium orbit model, the residence time model does not consider potentially important variables such as radial fluid flow, hindered settling effects, droplet coalescence or the effect of turbulence.
1.3.3
Empirical model
Coleman and Thew proposed the following empirical correlations for estimating the cut size of a hydrocyclone. HY75 xDc
XPC
d 7 , =[
QxAp
Where the hydrocyclone number H y , is defined by equation 1.6. The constants in this equation are determined empirically for each type of hydrocyclone. The constants given here were determined for the hydrocyclone studied in reference (31. H y , Where: c,
Cp
= c1x(Re,)'2
Eq. 1.6
= -0.15
= 0.011
Re, =
4xQxpc XXDCXPC
Eq. 1.7
1.4
Miaration probability
The separation performance or separation efficiency of a hydrocyclone can be described by the migration probability (MP). The migration probability for a droplet of diameter d is defined as the probability that it will be separated and leave the hydrocyclone in the reject stream. Pp(d)xCp x(1-R) Eq. 1.8
The reduced migration probability MP' is the migration probability independent of reject ratio, defined as; MP'(d)= 1-
"9"b-")xloo
Eq. 1.9
Puxe 1-2
SIPM Droilinfi Miiuiiid, EP 93-1315. Hrv 1.1, Nirv 1993. File iiriine = 99llCYCL.DOC
[ [
-(d", --
o.l15~]]xloo
Eq. 1.10
The second correlation is from Colman and Threw ( 3 1for use in conjunction with their empirically derived cut size correlations (1.5, 1.6). The constants in this equation are determined empirically for each type of hydrocyclone. The constants given here were determined for the hydrocyclone studied in reference [3]. MP(d) = 1- exp[ cg x[ 2 - c 4
Where:
cg c4 c5
= -1.8 = 0.19
,"'I])(
100
Eq. 1.11
= 1.25
1.6
where c6 and c7 are empirically derived constants. The same expression with different constants can be used for modelling both the feed-to-product stream and the feed-to-reject stream pressure drops.
1.7
1.7.1
1.7.2
OWTC trials
The empirical correlations of Colman and Thew (1.5, 1.6, 1.7, 1.11, 1.12) were applied to the results from the OWTC trials "Comparative testing of new generation deoiling hydrocyclones" [l]. Empirically derived values for the constants c, to c7 were determined for the Vortoil and Hydropak hydrocyclones, while constants c6 and c7 were correlated for all the tested hydrocyclone designs. The results are presented in Table 1.1
Table 1.1 Empirically derived constants to fit hydrocyclone modelling equations
Puxe 1-3
Nomenclature
d Di D ,
= = = 0 , = Hy = MP(d) = MP'(d) =
P(d) AP
Q
R
feed oil concentration (mg/l) droplet diameter (m) inlet diameter (hydrodynamical) (m) hydrocyclone body diameter (m) Vortoil nominal hydrocyclone body diameter (Db/2) hydrocyclone number (dimensionless) migration probability, the chance of a droplet with diameter d being separated (%) reduced migration probability (%) - number of droplets = volume fraction of dispersion of droplet size d = pressure drop (bar) = Volumetric flow rate (m3/h)
Qr = reject ratio R = Qf
Rei R e ,
P Ap
P
Subscripts
= Reynolds number at the inlet (dimensionless) = Hydrocyclone Reynolds number - fluid velocity (m/s) = density (kg/m3) = density difference between continuous and dispersed phases (kg/m3) = viscosity (kglm s)
feed stream at inlet product stream (water outlet) reject stream (hydrocarbons outlet) continuous phase
P U ~ 1-4 C
SlPM Duoiliii~ M ~ ~ i i i iEP d , 9.1-13 15, R i v 1.1. Niiv 1993. File i~iiiiic = 99IICYCL.DOC
J.l. Introduction
The following method for the prediction of the concentration of dissolved hydrocarbons in water has been extracted from the KSLA research note:
"NAM F3 produced water clean up. Solubility and stripping of aromatics in water", P.J.F.M. De Krom, KSLA EE/4, 28th Sept 1990, Ref.3.02.2.a
5.2.
Theory
The solubility of most produced hydrocarbons in water is relatively limited. Thus a mixture of liquid hydrocarbons and water will result in the formation of two phases, each phase containing a proportion of the other phase on the basis of solubility and equilibrium considerations. Under equilibrium conditions the chemical activity (a) of a hydrocarbon component i is the same in each phase. Eq. J.l The activity of each component is defined by; a=Xxy and the distribution coefficient (m) over the two phases is described as; Eq. J.2
m=[?]
Eq. J.3
m = [ ~ ]
Eq. J.4
For an ideal hydrocarbon mixture, if component i is a hydrocarbon, then the activity coefficient for component i in the hydrocarbon phase ( Y ~ , ~is ) equal to 1. For low hydrocarbon concentrations of component i in water, yj,w is virtually constant and can be taken as the same as for the pure component in water. Thus under the assumptions of ideal hydrocarbon behaviour and a low concentration of hydrocarbons in the water phase, equation J.4 simplifies to; m = y I.pure,w Substituting J.5 back into J.3, the solubility of component i in water can be expressed as; Eq. J.5
Eq. J.6
Puxe I-1
Eq. J.7
Thus the solubility of component i from a hydrocarbon mixture can be calculated from equations J.6 and J.7 as; Eq. J.8 Therefore, the solubility of hydrocarbon i from a hydrocarbon mixture in contact with water is equal to the molar fraction of that component in the hydrocarbon phase multiplied by the solubility of the pure hydrocarbon component in water.
In practice the hydrocarbon mixture is not ideal and the activity coefficient (yi,J is greater than 1. This causes the actual solubility in pure water to typically be 20 to 30% higher than the predicted value. In addition, the effect of other variables on the solubility such as salinity, temperature, pH and the presence of production chemicals in the water phase must be considered.
Nomenclature: a c m = activity (--) = concentration (ppm(w)) = distribution coefficient (--) = mole fraction in liquid (--) = activity coefficient (--)
Y
Subscripts:
h = i = pure = w =
..
Table J.l contrasts the theoretically and experimentally determined dissolved hydrocarbon concentration in water for a relatively complicated mixture of aromatic compounds. Table J.2 contrasts the theoretically and experimentally determined dissolved hydrocarbon concentration in water for a mixture of aromatic and aliphatic compounds similar to that which could be expected in condensate from a gadcondensate production operation. In both tables it can be seen that the theoretically predicted dissolved hydrocarbon concentrations are lower than the experimentally determined concentrations, by 10% and 24% respectively. However, Table J.3 illustrates the predicted and measured hydrocarbon solubility for two operating gas
PUXC J-2
SIPM Droilirix Motitid. EP 9.7-1315, Rev 1 1. Niiv 199.7. File nome = 99JJDlSS.DOC
- Phase equilibria
For guidance on the prediction of hydrocarbon solubility using simulation packages, reference should be made to; "Basic data and phase behaviour methods", DEP 20.00.1 0.1 0-Gen, April 93
J.4.
A "simple" mixture of aromatics was used to establish a base case solubility. The mixture was composed of 15 wt% benzene, 37 wt% toluene, 43 wt% xylene and 5 wt Yo ethylbenzene. The solubility was established as 696 ppmw at 1 atm, 25C and a pH of 7 Effect of pH When the pH of the water was lowered to 4.5 it was found that the level of dissolved hydrocarbons in the water increased by 8% to 753 ppmw. Considering the accuracy of the experiment this variation was not considered significant. Effect of temperature When the temperature of the water was raised to 50C it was found that the level of dissolved hydrocarbons fell by 4% to 670 ppmw. Considering the accuracy of the experiment this variation was not considered significant. Salt concentration The levels of dissolved hydrocarbons was measured for water salt concentrations of 17 g/l, 34 g/l and 51 g/l NaCI. The solubility was found to fall with increasing water salinity to 653 ppmw, 504 ppmw and 481 ppmw respectively. Presence of methanol 1000 ppmw of methanol was added to the hydrocarbon/water mixture of which 560 ppmw of the methanol dissolved in the aromatic phase. The level of dissolved hydrocarbons in the water (excluding the methanol itself) was found to increase by 40% to 974 ppmw. Presence of corrosion inhibitor When 400 ppmw of corrosion inhibitor was added to the hydrocarbon/water mixture the levels of hydrocarbons in the water phase increased dramatically by 180% to 1930 ppmw. When 30 ppmw of corrosion inhibitor was added to the hydrocarbon/water mixture the level of dissolved hydrocarbons in the water increased by 18% to 824 ppmw. However in both cases the water phase was not a clear liquid and these high levels of hydrocarbons may be a result of the formation of a stabilised emulsion of finely dispersed hydrocarbons in the presence of corrosion inhibitor and may not reflect true hydrocarbon solubility.
Component
Molar percentage
(%)
(ppmw)
%ax
Ctheoretical
(ppmw)
%emured
Error
(ppmw)
-60%
-10%
4 19
Table J.2 Comparison of predicted and measured dissolved hydrocarbon contents for a mixture of aromatic and aliphatic hydrocarbons Component Molar percentage
% a x Ctheoretical %easured
Error
(PPmw)
(PPmw)
(PPmw)
Benzene Toluene Ethylbenzene Xylene i-propylbenzene n-propylbenzene o-ethyltoluene n-butylbenzene n-heptane i-octane naphthalene
I
1760.0 542.0 165.0 180.0 50.0 52.2 93.1 13.8 2.24 0.43 32.1
Totals
I
44 26 1.3 8
<1 <1 <1
<1
1 1 1
PI
79
PI
-24%
[ I ] The solubility of paraffins and naphlhalene could not be mea ired in the G c
PU#C
f-4
SIPM Deoiliiix MoiiiioI, EP 93-1315, Rev 1.1. Nov 199.3, Filr ii(liiie = 99JJDISS.DOC
Table 5.3 Comparison between predicted and measured concentrations of dissolved hydrocarbons for actual platform production water Platform Predicted soluble aromatics (ppmw) 190 386
I I
Error
Platform 1 Platform2
-8.5% +2.1%
Table J.4 Hydrocarbon solubility in water at 25C and 1 atm Formula Name M.W. Boiling point ("C) -161.5 -88.5 -42.0 -0.2 -11.6 36.1 28.0 80.1 68.8 110.6 98.4 136.0 139.1 144.3 138.3 125.6 165.1 150.7 218.0 183.3 173.7 Solubility in water (ppmw) 24.4 60.4 62.4 61.4 48.9 38.5 47.8 1760.0 13.3 542.0 2.24 165.0 174.0 221.o 202.0 0.431 52.0 50.0 93.1 0.122 32.1 13.8 0.052 iopper, J.R.,
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17' 18' 19 20 21 22 23
CH4 C2H6 C3H6 C4H10 C4H10 C5H12 C4H12 C6H6 C6H14 C7H8 C7H16 C8H10 C8H10 C8H10 C8H10 C8H18 C9H12 C9H12 C9H12 C9H20 C10H8 C10H14 C1OH22
Methane Ethane Propane n-Butane i-Butane n-Pentane i-Pentane Benzene Hexane Toluene Heptane Ethylbenzene m-Xylene @Xylene p-Xylene Octane n-Propylbenzene iPropylbenzene o-Ethyltoluene Nonane Naphthalene n-Butylbenzene Decane
16.043 30.069 44.096 58.123 58.123 72.150 72.150 78.1 13 86.177 92.140 100.203 106.167 106.167 106.167 106.167 114.230 120.194 120.194 120.194 128.257 128.173 134.221 142.284
--..---.--
Source: "Hydrocarbons: Water solubilii data", Yaws, -., Yang, H.C Hansen, K.C., Chemical Engineering,A il 1990, p177-182
* Source not identified, taken from KSLA reoort "NAM F3 DrodUCed water clean UD. Solubility and stripping of aromatics in water", 'P.J.F.M. De Krorn, KSLA EE/4, 28th Sept
1990
Table 5.5 Results from KSLA hydrocarbon solubility trials Variable Test conditions Dissolved hydrocarbons in water (ppmw) 696 753 670 653 504 48 1 Variation from base case
25%, pH=7, latm, OgA NaCl Base case + pH=4 Base case + 50C Base case + 17 gA NaCl Base case + 34 gA NaCl Base case + 51 gA NaCl Base case + 1100 ppmw methanol Base case + 400 ppmw corrosion inhibitor Base case + 30 ppmw corrosion inhibitor
N/A
8%
-4%
-6% -28% -31% 40% 177% 18%
PUKE J-6
SlPM Denilinx M i i n i d EP 93-1.715, Rev 1.1. Nov 1993, Filr ncime = 99JJDISS.DOC
K.l.
Introduction
The comparison tables presented in this Appendix have been extracted from the following reference. A comparison of oily water separation technologies, Jan Dec 1992, Buss, G., Visser, R., Rye, A., Lawrence, A., SlRM report number AMGR.92.340, SIPM report number EP 93-0651. These tables have been provided to allow the user to compare the relative sizes, capital costs and operating costs of a number of alternative methods for the removal of dissolved hydrocarbons Users should be careful not to take this information out of context. The results from the comparison will be strongly influenced by the design basis and the assumptions made in equipment selection and sizing. In particular, the integration of the treatment system into the overall process will have a significant impact on the cost effectiveness of any treatment package. Factors such as the disposal or regeneration of secondary streams or the availability of utilities such as nitrogen or steam may strongly influence the suitability of a given scheme. Costs reflect 1992 prices and will naturally change with both time and technological improvements to the equipment. All the processes presented in this appendix are discussed in more detail in chapters 9 and 10.
K.2.
Desian basis
All equipment sizing was based on nominal water flow rates of 4.2 mVh, 42 m3/h and 420 m3/h (100 mVday, 1000 mVday and 10,000 m3/day respectively). The water was taken as contaminated with 500 mg/l of benzene with a required effluent benzene specification of 10 mg/l. The water temperature was assumed to be 35C. With the exception of a water filter on the water feed stream, no allowance has been made for any upstream processing which may be required. Normally, upstream processing would be -required to remove the majority of the dispersed hydrocarbons and solids. Treatment or disposal of stripping streams is a parameter which must be carefully considered in the design and operation of a facility for the removal of dissolved hydrocarbons. As it is system dependent, in this comparison no consideration has been given to the treatment or disposal of stripping streams. Allowance has been included for piping, electrical, instrument and structural bulks. Specific inclusions and exclusions for each system are documented below. Air stripping: Nitrogen stripping: Simple atmospheric air stripping column. Includes column, water feed pump, air blower, water filter and column packing. Similar to air stripping column. Includes a capital cost for a nitrogen generation plant. Includes column, water feed pump, water filter and column packing. Based on recompression of the stripping gas to circa 65 barg. Includes column, water feed pump, water filter, column packing and suitable multiple stage compression system with associated coolers and scrubbers. Assumes an external source of steam is available for use in the stripping column. Allowance is made for the column, water feed pump, water filter, column packing, overheads condenser, reflux drum and feed preheater. Uses a reboiler to produce steam from the product water stream. The system is designed to operate under vacuum to improve the stripping and lower the boiling temperature, Allowance is made for the column, water feed pump, water filter, overheads condenser and reflux drum, feed preheater, reboiler,
Gas stripping:
Puxe K-I
Nanofiltration:
Airlift bioreactor:
Solvent stripping:
K.3.
Results
The capital costs, operating costs, weights and power consumptions of the different equipment configurations, based on the assumptions and definitions outlined above is presented in the following tables.
Table K.l Capital costs of equipment for the removal of dissolved hydrocarbons (US$, Jan 1992) Process Water flow rate (m3/h) 42 I
4.2
420
Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofittratiin Airlift biotreater Solvent stripping
________________
2,000,000 970,000
Puxe K-2
ii~ine =
99KKCOMP.DOC
Table K.2 Annual operating costs of equipment for the removal of dissolved hydrocarbons (excludes energy costs) (UWyear, Jan 1992) Process Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofiltration Airlifl biotreater Solvent stripping
1.
7-p+
23,000 80,000 60,000 36,000 52,000 80,000 70,000 36,000 40,000 32,000 190,000 170,000 73,000 75,000 370,000 300,000 150,000
420
-_________-_____
Source: 'A comparison of water separation technologies", In - Dec 1992, Buss, G., Visser, R., Rye, I Lawrence, A,, SlRM report number AMGR.92.340, SlPM report number EP 93-1
Process Dry Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofiltration Airlifl biotreater Solvent stripping
4.2
Wet
Dry
420
Wet
10 10 2 1 20 1 9 18 20 10 7.9
15 14 26 25 24 2 1 22 19 8 . 1
__-_55 34
13 1 2 76 30 28 26
-----
23 2 1 85 38 37 30
'
140 35
SIPM Dwf11tfg Mof~riol. &P 93-1315. Rrv I I . N ~ 1993. V File ii(iiife = 99KKCOMP DOC
Puge K-3
Table K.4 Power requirements of equipment for the removal of dissolved hydrocarbons (kW) Process Air stripping Nitrogen stripping Gas stripping Open steam stripping ( 1O O O C ) Closed steam stripping (35C) Pervaporation (35C) Nanofiltration Airlift biotreater Solvent stripping
e
4.2 5
4
- 42
11
420
34
82
84
84
Note
Includes: Blower and feed pump electricity Excludes: Further VOC and water treatment, nitrogen generation 1,520 Includes: Pump and compressor electricity Excludes: Further water treatment
7,780 Includes: Electricity and steam 7,550 Includes: Electricity and steam 7,550 Includes: Electricity and steam
1 . 5 22
2
176
1. Power reauirements similar to air sti 2. VOC = Volatile organic compounds 3. Source: 'A comparison of oily water separation technologies", Jan Dec 1992, Buss, G.,Visser, R., Rye. A., Lawrence, A,, SlRM report number AMGR.92.340, SlPM report number EP 93-0651
Puxe K-4
iiiiiiir
= 99KKCOMP.DOC
. .
. .
..... .
...
. .
L.l.
Introduction
The discussions in the following sections give a brief summary of the commercially available membranes that have been recently tested by Shell though Opco or OWTC trials. The majority of the information has been taken from the following two OWTC trials: "Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd, Phase I , 15 April 1991. EP-no. 91-1017 Four membranes were examined in the Phase I trials: Alcoa Petrolox, SDI, Stork-Wafilin and X-Flow. The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, concentration, droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals, gas breakout, and scale forming compounds.
0
"Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd", Phase II, 20 September 1991, EP-no. 91-2152 Three membranes were examined in the Phase II trials: WL Gore, Schelde Delta and SDI (modified since Phase I trials). The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, oil droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals and scale forming compounds. The report also investigated the performance of the Wemco Silver Band crushed nut shell deep bed media filter.
However the membranes discussed in this appendix do not represent the complete range of membranes that could potentially be used for the removal of dispersed hydrocarbons from water. Reference 2.15.1 .h from the bibliography contains a listing of other membrane manufacturers who are potentially involved with the production of membranes for waste water treatment.
L.2.
Alcoa Petrolox
The Petrolox system is a packaged unit containing Alcoa Membralox membrane elements. The Membralox elements are made from alumina and shaped as hexagonal prisms with flow channels running through the element. The bulk of the element is supporting substrate, however the inner surface of the channels has a thin ceramic layer with the desired pore size. This thin layer acts as the membrane. A range of pore sizes are available from 0.2 pm to 12 pm (12 pm = substrate only). A 0.8 pm pore size is usually used for deoiling duties. The filter is automatically cleaned every 2 to 6 minutes by sending a back-pulse of clean permeate through the system for a duration of 0.5 to 2.0 seconds. This helps dislodge accumulated hydrocarbons and solids from the surface of the membrane so they may be carried away. Dosing of ferric chloride and sodium carbonate in the oily water feed is used to improve the flux and life of the membrane by precipitating fine solids to act as a filter aid. Dosing requirements can be reduced if suspended solids are present in the feed stream. When the flux declines to unacceptable levels the membrane can be chemically cleaned. The alumina structure allows a wide range of chemical cleaning agents to be used. The Alcoa Petrolox system has been tested at the OWTC, achieving a permeate quality of 1 to 29 mg/l of hydrocarbons with a typical level of 10 mg/l. Permeate quality was higher for heavier oils (2 mg/l for 21" API oil). Chemical cleaning was effective with the unit returning to a "clean" condition. Testing was also conducted at Nam with similar results to the OWTC.
A number of trials of the Petrolox system have been conducted in the USA and two 1000 m3/d full scale units have been installed. These have indicated that the system can achieve hydrocarbon levels below 5 mg/l, however the installations require a significant amount of operator attention to achieve reliable performance. Fouling has been variable. The potential impact of recycling hydrocarbon concentrate must be evaluated as the recycle stream will contain the precipitated ferric chloride which may affect the stability of oil/water emulsions.
SDI Extran
The Separation Dynamics Inc (SDI) system uses the cellulose based Extran membrane. This membrane is a non porous type, fashioned in the form of hollow fibres. The fibres are collected into bundles and packaged into pressure vessels. The oily water feed flows through the inside of the fibres with water diffusing through the membrane to the outside of the fibres for collection. Because the membrane does not contain pores it is claimed to be quite resistant to fouling. However as the flux rate through the membrane is governed by diffusion, the flux rate per unit area of membrane is relatively low, in the order of 30 times lower than the porous ceramic membranes. The SDI Extran system has been tested at the OWTC, achieving a permeate quality of 4 to 30 mg/l of hydrocarbons with a typical level of 10 mg/l.
A recent trial of the SDI system by Expro (Ref.2.15.2.f) demonstrated that dispersed hydrocarbons in the order of 1000 to 20,000 mgA were reduced to 10 5 5 mg/l. Dissolved aromatics in the order of 700 to 7000 mg/l were reduced to 300 rt 50 mg/l, though the extraction effect of the concentrated dispersed hydrocarbons is thought to be the dominant influence on the removal of dissolved hydrocarbons. Only slight fouling was observed.
L.4.
X-Flow
The X-Flow membrane is a polyethersulphone capillary tube membrane of 0.2 pm pore size. The system is designed for automatic backflush and chemical cleaning. The X-flow system was tested at the OWTC, achieving a permeate quality of 1 to 18 mg/l of hydrocarbons with a typical level of 8 mg/l. One X-Flow membrane tested had an adverse reaction with corrosion inhibitor, though this was corrected with a modified membrane. Fouling was experienced using the 1.0 mm capillary membranes, through better results were obtained with the 1.5 mm membranes. In operation the flux declined to 50% of the rated flux rate. The X-flow system has also been tested by M a s k , obtaining low levels of hydrocarbons in the permeate. However operation problems were experienced with fouling and degradation of the membrane material.
L.5.
L.6.
Schelde-Delta
The Schelde-Delta membrane system is a ceramic alumina membrane on a silicon carbide support medium. Tests at the OWTC indicated a permeate quality of 13 to 68 mg/l with a typical level of 20 mg/l. The performance of the system was significantly upset by the presence of corrosion inhibitor and demulsifier.
L.7.
WL Gore
The WL Gore design uses a tubular expanded PFTE oleophilic membrane. Tests at the OWTC indicated a permeate quality of 6 to 30 mg/l with a typical level of 11 mg/l. Flux rates declined to 20 % of the rated flux rate.
L.8.
Hoouovens
The Hoogovens design uses an alumina ceramic membrane. The system was tested by NAM (as a simple trial unit) with encouraging results. However, further testing with a more complete packaged unit gave variable results with permeate quality in the order of 40 mg/l.
P q e L-2
SIPM Drri;liii~ Monrrrd. Et' 93-1315, Rev 1.1, Niiw 1993, Fi/r iwnr = 99LLMEMB.DOC
P U , ,
L-4
SIPM Dwi/;iix Mtriiutil. Et 93-1315, Rev 1.1. Nov 1993. File iitiriie = 9YLLMEMB.DOC
Bibliography
. . . . . . . . .
1.
Introduction
The following bibliography lists the sources of information used in the update from the SlPM Dehydration/Deoiling Manual EP 89-0150 to this Deoiling Manual. All referenced information has been archived at SlPM EPD/42 and can be requested if not available from local sources.
2.
Literature searches
Literature searches have been made on the SlPM Stairs database to identify internal reports and papers relevant to deoiling. The following keyword combinations were used for the literature search. water
AND
treatment
AND
water$
deoiling
AND
epr
NOT
AND
epr
AND
(injection disposal)
NOT
(treatment watertreatment)
ADJ in ADJ
(water waters)
AND
epr
NOT
(treatment watertreatment)
caisson$
3.
Index
All the references in the Bibliography include a short description of the reference and an identifying reference number.
The references are grouped in numerical order. As each topic has a unique reference number, all the references on a given topic will be grouped together. For example, all references to hydrocyclones are grouped together under the reference number 2.05.X.X. The following table presents an index to the topics included in the Bibliography.
INDEX TO BIBLIOGRAPHY
1. GENERAL
1.1........Produced water analyses, legislation 1.2 ........ Water analysis methods 8 standards 1.3 ........ Oil-in-wateranalysers Size particle analysers 1.4 ........ 1.5........ Treatment chemicals 1.6 ........ Ballast waters Sampling 1.7........ 1.8........ Emulsions 2. DISPERSED HYDROCARBONS
2.12 ...... Pre-coat filtration 2.13 ...... Cartridge filtration 2.14 ......Coalescers 2.15 ...... Membranes 3. DISSOLVED HYDROCARBONS 3.1 ........Dissolved hydrocarbons .General 3.2 ........Stripping 3.3 ........Biologicaltreatment 3.4 ........Carbon adsorption 3.5 ........ Solvent extraction 3.99 ......New technologies
OTHER INFORMATION
2.1 ........Dispersed hydrocarbons - General 2.2 ........Inducedgas flotation 2.3 ........API separators 2.4 ....... Plate packs 2.5 ........ Hydrocyclones 2.6 ........Skim tanks 2.7 ........Deep bed filtration 2.8 ........Centrifuges 2.9 .......Dissolved gas flotation 2.1 0 ......Caissons 2.1 1......Rotary cyclones
Bib1iograp hy
BIBLIOGRAPHY
- REFERENCE LISTING
DESCRIPTION OF REFERENCE
REFERENCE TITLE
Characteristics of Production Waters, Merville, E.de, Presented at the Regional Seminar on Technical Aspects of Oily Water Discharges, Bahrain, Nov 1982, The Oil lndustry lnfernational Exploration & Production Forum The composition of produced water from Shell operated oil and gas production in the North Sea, Jacobs, R.P.W.M., Grant, R.O.H., Kwant, J, Marquenie, J.M., Mentzer, E., lnfernational produced wafer symposium, Feb 4-7, 1992, San Diego Characterisation of residual hydrocarbons in produced water discharged lrom gas production platforms, Callaghan, D, Baumgartner, W., Society of Petroleum Engineers paper, SPE 20881 Environmental effect of produced water from North Sea Oil operations, Someiville, H.J., Bennett,D., Davenport, J.N., Holt, M.S., Lynes, A., Mahieu, A., McCourt, B., Parker, J.G., Stephenson, R.R., Watkinson, R.J., Wilkinson. I.G., Marine Pollution Bulletin. VollB/Nurnber IO,Oct 1987 A comprehensive determination of produced water composition, Tibbets, P.J.C., Buchanan, I.T., Gawel, L.J., Large, R., lnternationalproduced wafer symposium, Feb 4-7, 1992, San Diego Characterisation of produced water discharges, Conoco presentation, 14/1/9 1 Waste management programme -Analysis of North Sea overboard water discharges, Lynes, A,, McCourt, C.B., Thornton Research Centre, April 1991, TNGR.91.014, ep-no.91-0832 A survey of produced water studies, Stephenson, M.T., lntemationalproduced wafer symposium, Feb 4-7. 1992, San Diepo Shell Expro's Wastes 1989 Recommended practices for the monitoring and recording of effluents and wastes in E&P operations, Oct 89, Report EP 892460 Characteristics of refinery wastes, extracted from API Manual on Disposal Of Refinery Wastes, Chap 13 Section 1. Information in water pollution, extracted from API Manual on Disposal Of Refinety Wastes, Chap 2 Components of produced water: A compilation of industry studies, Stephenson, M.T., Journal of Petroleum Technology, May 1992 Environmentalaspects of platlorm discharges: Part II Monitoring of inorganic discharges lrom Brent and Dunlin platforms, McCourt, C.B., TNOR.86.035, EP 86-1136, Dec 86 Waste management programme Analysis of North Sea overboard discharges Part 2, Lynes, A., McCourt, C.B., Thornton Research Centre, March 1992, TNGR.92.045, epno.92-0727 The environmental impact of refinery effluents, Concawe's assessment, Concawe report 1/80, Feb 1980
Reference
number
Ref.l.Ol.1.a
Discusses the distinguishing characteristics of production waters. Basis for tables presented in chapter 2 discussing the relative contributions of dissolved, dispersed and polar hydrocarbons in water. Discusses the characteristics of water discharges lrom gas platforms, relative amounts of dissolved and dispersed hydrocarbons, droplet size distributions, effect of corrosion inhibitor. Written by Shell personnel, discusses the composition of the water effluent discharges from a number of North Sea platforms, the toxicity of the effluents as measured in the laboratory and in the environment and the dispersion characteristics of the effluent in the ocean. Discusses the methods used to identify 5 groups of characteristics of effluent water from several North Sea platforms, 1) Physical parameters, 2) Petroleum hydrocarbons, 3) Minerals, salts and metals, 4) Non hydrocarbon organics, 5) Treatment chemicals. Presentation covering the work and results of characterising produced water discharges lrom Murchison and Hutton platforms. Delves into analytical methods and treatment chemicals. Gives the analysis 01 the effluent streams from the Expro North Sea platforms, including organics and heavy metals. Claims there are significantly more treatment chemicals being used. Relatively simple discussion collecting the results of a number of oily water surveys together. Detailed report quantifying and discussing all waste streams from Shell Expro for 1989. Covers the grading 01 various materials in terms of toxicity and the general practices that should be followed for monitoring all effluents. Discusses the characterisation of waste waters such as various oxygen demands, typical contaminants, heavy metals, temperatures etc. Discusses the environmental impacts 01 waste waters including oxygen content, turbidity, pH, oil concentration, Discusses the contaminants present in produced waters including hydrocarbons, heavy metals, radionuclides, and treatment chemicals. Also discusses the potential environmental effects of these chemicals, Results lrom a sampling and analysis program. Furthers part I work (1.Ol.l.g) in identilying unknown organic material as naturally occurring humic acids. Discusses the range of contaminants in refinery discharge water in Europe and discusses the potential environmental impacts. Discussion on the problems faced when meeting effluent limits lrom gas platforms, Document not referenced. Unrelerenced discussion of the NOGEPA view on water discharges. Discussion on the magnitude and distribution Of various sources of pollution in the North Sea. Discusses the history of the Parcom standard, its current implementation and the development of uniform standards for its application. Discuses a range of water standards lrom drinking water to 1 water for industrial use. Only useful as background information. Discusses the introduction of the new 29 mg/l discharge levels in the USA. Comments that the new levels are based on the expected performance lrom improved induced gas flotation
Ref.l.Ol.1.b
Ref. 1.01.1 .c
Ref.l.Ol.1.d
Ref.l.Ol.1.e
Ref.l.01.1 .f
Production water from gas/condensate platforms, Discussion on limits lor oil content, 1st draft, 1986, Not referenced Water discharged from offshore platforms, The NOGEPA view, Not referenced Oily water discharges from offshore North Sea installations: A perspective, Read, A.D., Blackman, R.A.A., Marine Pollution Bulletin, Vol.11, pp 44-47 The origin and development of the PARCOM provisional target standard, Read, A.D., E & P Forum report 2.43143, Dec 1987 United Kingdom water quality standards arising from European community directives, Gardiner. J.. Mance, G.. Julv 1984 New produced water guidelines to impact U.S. operations significantly, Bell, S., Petroleum Engineer International, May 1993.
Pu,qe Biblio~,qruphy-2
Bibliography
A protocol for determining oil and grease in produced waters, Simms, K., Zaidi, A., Bhargava, O., lnternationalproduced water symposium, Feb 4-7, 1992, San Diego On-site testing of oilfield waters, Robinson,K, Society of Petroleum Engineers, Paper SPE 14128, 1986 PD Oman oil-in-water measurements, Bannell, J., Personal communication Norwegian standard for oil in water analysis, NS 4753, unofficial English resume DIN 38 409 Part 18: German standard methods for the analysis of water, waste water and sludge, Determination of hydrocakons Determination of hydrocarbons in aqueous effluents from the oil industw by infrared analysis, Concawe report 1/84 NEN 6675: Water Bepaling van he1 gehalte aan minerale olie Oct 1989 met behulp van infrarood-spectrofotometrie, (Water Determination of mineral oil content by infrared spectrophotometry) Measurement of oil in effluent water discharged from Shell Expro platforms. A review of sampling and analysis methods, Booth, S., Well engineering information note WEIN/3269, 15/6/92 Good discussion on the limitations of current analysis procedures and the search for a suitable replacement to Freon 113 Written by Oil Plus, discusses the methods used for analysis of oil field waters, including sampling, solids, particle sizing, core tests, scale and corrosion inhibition Recommends the use of mgA as the unit for measuring oil in water over the use of ppm. Also discusses in general terms various aspects of measuring oil in water levels. Unofficial translation from Norwegian into English. Resume only German standard for measurement of hydrocarbons in water. Excellent text covering most aspects of measuring oil in water, including tables of all the existing methods etc. Dutch standard for measuring oil in water, published Oct 1989 Ref.l.02.l.a Ref.l.02.l.b Ref.1.02.l.c Ref.l.02.1 .d Ref.l.02.l.e Aef.1.02.1.f Ref.l.OP.1.g
Methods of analysis and sampling of oil in water, Oldham, G.F., E B P Forum report 2.33/115,1985 Determination of Total Hydrocarbons in Water, Rotteri, S. Concawe article, presented as the Workshop on the Chemistry and Analysis of Hydrocarbons in the Environment, Barcelona, Nov 81 How to improve the accuracy in the EPA static sheen test, Weintritt, D.J., Qaisieh, N.S.. Otto. G.H., Oil and aas journal API recommended practice for analysis of oil field waters, API RP 45, JUIV 1981 Analysis of trace elements (heavy metals) in produced water, Personal communication from KSLA Environmental monitoring of trace elements in water discharged from oil production platforms, McCourt, C.B., Peers, D.M., Petroanalysis'87, Edited by Crump, G.B., 1988 John Wiley & Sons Environmental aspects of platform discharges: Part 1 Development of an analytical methodology for analysis of inorganics in production waters, Williams, G., McCourt, C.B., TNOR.85.023, EP 06-3621, Sept 85 633 organic chemicals: Surface tension data. Chemical Engineering, March 1991 Oil in water on line analysers, A survey of operating experience in the oil exploration and production industry, E & P Forum report, 2.27/109, Oct 85 An on-line method for the detection and measurement of oil in water discharges, Bannell, J.L., van Deelen. C., KSEPL, prepared for the 1992 Production and process technology conference, The Haque, Oct 1992 Laboratory evaluation of the Baird Petrolarm oil-in-water monitor, Willigers, M.C., der Kinderen, W.J.G.J.. Nov 88, KSEPL RKOR.88.027, EP 88-2562 Laboratory investigation of the AEG-Oili-Si000 Mark C oil-inwater monitor, Williaers. - . M.C... KSEPL RKGT.90.115. EP 903029. Short evaluation of the Horiba OCMA 25 oil-in-water monitor, Scheers, A.M., KSEPL RKER.84.133, EP 61044, May 84
Reviews the water sampling and measurement procedures at all Expro platforms, also a brief description of the water treatment facilities on each platform. Recommends moving to IR analysis and better sample points. Discusses practical problems in sampling and analysis Brief paper summarising the basics of the infrared analysis procedures Discusses the EPA sheen test used in the USA for assessing the level of hvdrocarbons in drilling muds and wastes. Covers a range of procedures for most common production water analyses. Brief covers recommendations for sampling and presetvation of samples containing heavy metals Discussion into the methods and analysis techniques used for the monitoring of trace elements from the Shell Expro platforms. Discusses the techniques required for sampling, preservation and analysing discharge waters. Data and methods for the prediction of surface tension. Discusses the application and problems experienced with monitors in the field Discusses the current KSEPL development of a oil in water monitor utilising short wavelength infra red light. Presents encouraging results and work is continuing. Test of a UV fluorescence based monitor. The test was not considered successful. Meter gave good results for measuring oil concentration, however was too sensitive to chanaes in water temDerature and not built to suitable industrial iandards. Considered the instrument to give good results. Not sensitive to aromatics. Some modifications required to exclude solids to extend the service life of the filters. Numerical investigation into the use of determining particle size distributions by optical density measurements
Ref.l.OZ.1.h
Ref.i.02.1 .i Ref.l.02.l.j
Ref.l.02.2.d
Ref.1.03.2.a Ref.l.03.2.b
,
I
Characterisation of particle suspensions by spectral extinction: A numerical study, Wilkinson, D.. Waldie, B., Powder technology, 68 (1991) pp 109-115 Laser particle sizing, Butcher, C., The Chemical Engineer, 11 Oct 1990, p 34 Droplet size distribution analysis with an image-analysis system, Oil/waler separation, (1989-1 990), Molenaar, H.J., Fens, T.W., Bonnie, J.H.M., AMGR.90.108, EP-No.90-2982 The use of on-line optical devices for measuring oil in water content, Colman, D.A., Thew, M.T., International conference on Optical Techniques in Process Control, The Hague, June 1983 Galai CIS-1000 test report, H.P. Visser, R.M. Visser, AMGR.93.274 Vortoil DlOO Analyser and Galai CIS-1000 Opus particle size analyser, Opus UK Chemical Notification Scheme, 1993
Short discussion of the use of lasers and optical methods for particle size analysis. Discusses the KSLA method of determining droplet size ,distribution using the process of microphotography and computer assisted image analysis. Discusses the successful use of the Oilcon meters for measuring oil content from the discharge of a hydrocyclone. KSLA test of the Galai particle size analyser. Performance was generally good but operating envelope of instrument needs better definition. Galai brochures. Preliminary information for Vortoil for oil measurements. Also Fax from Vortoil confirming 80 barg design pressure, soon to be increased to 120 barg. Brochures on ultrasonic particle size analyser, could potentially be used for on-line particle size measurement of water in oil as medium does not have to be transparent. Presents the method used to categorise process chemicals used in the UK production industry and gives a guide to their
Noli
IY9.7. Filr
I I I ~ I I I= Y
99ZZ111Il.I~OC
Puac Oibliogrupliy-3
Chemical treatments and usage in offshore oil and gas production systems, Hudgins Jr, C.M., Journal of Petroleum Technology, May 1992, Review of speciality chemicals used for the treatment of produced fluids, van Laar, H.G., SIPM, EP-53975, not dated Desianina and selectina demulsifiers for ootimum field perfcirmaice based on production fluid characteristics, Berger, P.D., Hsu, C., Arendell, J.P., Sociefy of Petroleum Engineers, SPE 16285, 1987 Improved demulsifier chemistry: A novel approach in the dehydration of crude oil, Staiss, F., Bohm, R.. Kupfer, R., SPE Production engineering, Auq 1991 Deoiling chemicals for crude oil-in-water emulsions, Mitchell, R.W.. A u 1973, ~ EP 04-5055 Standard practice for coagulation-flocculation jar test of water, ASTM D 2035-80 Surfactants: Super molecules, Samdani, G., Chemical Engineering, March 1991 Flotation aid composition and method of use thereof, US Patent 5,151,195, Sept 1992, Petrolite Corporation List of suppliers of oil field chemicals, April 93 Welchem deoiler field trials in Marmul (MMPS), Report BDD/166/92, McKay, A,, June 92 A laboratory investigation 01 corrosion inhibitors for gas production, Glendinning. D., SPC/2, March 1989, NAM The tanker industry in the 199Os, Shell Briefing Service, Number 5 1991 Ballast water. Extract from API Handbook on Refinery Wastes, Chapter 7 Environmentalaspects of the gravity based structure F3-FB, Aarts, J.L.J., June 89, NAM Report 16.813 Sampling of liquid effluents from refineries, Concawe report, July 1980, Report no 7/80 Slandard practice for manual sampling of petroleum and petroleum products, ASTM D 4057-88 Standard practice for automatic sampling of petroleum and petroleum products, ASTM D 4177-82 On-line process stream analysis Sample take-off and transportation, Shell DEP 32.31.50.10-Gen, March 1992 Measurement of oil in effluent water discharged from Shell Expro platforms. A review of sampling and analysis methods, Booth, S., Well engineering information note WEINl3269. 15/6/92
Discusses treatment chemicals typically used offshore and their potential environmental impacts. Discussion covering all commonly used types of treatment chemicals. No date given but suspected to be pre 1986 Discusses the basic principles behind the function and selection of demulsifiers for Crude oil dehydration. Discusses development of new polyester amine demulsifiers which are claimed to have better performance than existing demulsifiers. Good discussion on the use of deoilers, however report is relatively old. ASTM Standard General discussion on new types of surfactants Patent application concerning novel chemical compositions useful as a filter aid. Discusses the use and mechanism of such aids in flotation systems. As forwarded to Hocal Discusses some theory and field trials of the use of deoiling chemicals with IGF, FWKO and a Hydromation filter. Discusses the testing of emulsion forming characteristics of several corrosion inhibitors for gas operations. Finds some are better at not stabilising emulsions than others and recommends field trials with the best chemicals from the tests. Discusses the tanker industry and the use of double skin hulls, segregated ballast Discusses the requirements for a ballast water treatment system suitable for a land based terminal. Discusses the levels of contamination expected in the ballast water from a proposed GBS (includes calculations) Discusses a wide range of aspects associated with sampling including isokinetic sampling, sampling solids and automatic samplers ASTM Standard ASTM Standard Shell DEP for sample points for on line analysers Reviews the water sampling and measurement procedures at all Expro platforms, also a brief description of the water treatment facilities on each. Recommends moving to IR analysis and better sample points. Discusses the specifications and use of the KSEPL transparent sampling bottle ASTM Standard ASTM Standard ASTM Standard Discusses the errors introduced when sampling slurries from the pipe wall. Indicated that velocities higher than the isokinetic velocity may be preferable. However, also showed that error was lower for smaller particles with less inertia. Investigation of sampling errors arising from sampling slurries using a probe. Illustrates the influence of some aspects of the probe design. Discusses the sample points used by Expro, particularly those used on North Cormorant for measuring droplet size distributions. Recent SlPM guidelines discussing alliorms of sampling: Tends to refer to existing Dehydration and Deoiling manual for sampling of water streams, but contains some useful information and guidelines. Illustrates typical simple probe designs and recommends samples are taken at least D/3 away from pipe wall. Also discusses sample containers. Similar to 1.07.1 .n above, applies to automatic sampler designs.~~ Extract from report AMTR.88.002
~~
Instruction manual, Transparent pressure sampling bottle for online stability tests of oiVwater mixtures in production systems, Aug 1985, Mandersloot, W.A.J., Stadt, M.E. van de, KSEPL RKMR.85.012, EP no. 6391 1 Standard Practices for Samplina of Waterborne Oils, ASTM D 4489-85 (Reapproved 1990) Standard Practices for Sampling Water, ASTM D 3370-82 Standard Specification for Equipment for Sampling Water and Slream, ASTM D 1192-70 (Reapproved 1977) Wall sampling in slurry systems, Nasr-el-din, N., Shook, C.A., Esmail, M.N., The Canadian journal of Chemical Engineering, Vol63, Oct 85 lsokinetic probe sampling from slurry pipelines. Nasr-el-din, N., Shook, C.A., Esmail, M.N., The Canadian journal of Chemical Engineering. Vol62. Apr 84 lsokinetic sampling at Expro, Personal communication from Booth, S., Jun 93 Guidelines for manual; sampling and analysis of hydrocarbon fluids, Steenson, B.E., EP 92-0980 Petroleurn products Liquid hydrocarbons Manual sampling, IS0 3170, First edition, 1975-07-01 Petroleum products Liquid hydrocarbons Automatic pipeline sampling. IS0 3171, First edition, 1975-12-01 Diagram from North Cormorant trials (2.05.2.h) indicating set-up of isokinetic sample quill through 2' ball valve. Turbulent pipe flow of dilute liquid-liquid dispersions: Drop sizes and criteria for homogenous BS&W distribution, Technical Progress Report WRC 197-76, Shell Development Co., A.. Karabelas, Dec 76, EP 04-8081
~~ ~
Ref.1.07.l.f
Standard practice for Preservation of Waterborne Oil Samples, ASTM D 3325-90 Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents, ASTM D 3694-92
Interesting report discussing the flow velocities required to obtain a representative sample of BS&W in oil. Shows that a given velocity must be maintained to ensure the droplets are fully dispersed. Even suggests sampling at 20% below the pipe centre line in some cases. ASTM Standard ASTM Standard, gives detailed procedures on the cleaning of both glass and HDPE sample bottles
Ref.1.07.2.a Ref.l.07.2.b
SlPM DridiiiK Mo~irirtl, EP 93-1315, Rev 1.1. N i w 1993, File numr = 99ZZBIB.DOC
__
Bibliography
Standard Practice for Estimation of Holding Time for Water Samples Containing Organic Constituents, ASTM D 4515-85, (Reapproved 1990) Emulsions, Fundamentals and applications in the petroleum industry, edited by Laurier L. Schramm, SlPM Library VH 92-1, 1991, ISBN 0-8412-2006-9 Emulsions: Theory and practice, Paul Becher, 2nd Ed, SlPM Library HI 65-2,1965 Encyclopaedia of emulsion technology, edited by Paul Becher, Vols 1 to 3, SlPM Libraw HI EET-1 to EET-3,. 1983, ISBN 08247-1876-3 van Beest, W.J., Jan 1969, KSEPL RKGR.0006.69, EP 04-0068 General review of Shell's plants and facilities for production water treatment, van der Velden, J., Sept 1986 Theory of separation, Excerpt from Alfa Lava1 laboratoly separation LAPX 202 users guide. Designing oil and gas production systems: How to size and select water treating Arnold, K, Stewart Jr, M. World - equipment. . . Oil, March 85 Designing oil and gas production systems: Selecting a waste water treating system, Arnold, K, Siewart Jr, M. World Oil, May 85 Desiqn conceot for offshore Droduced water treatinq and disposal systems, Arnold, K.; Journal of Petroleumkechnology, Feb 83 Response of an oil/water containing vessel to imposed motion. Theoretical and experimental modelling, Waldie, B., White, G.trans IChemE, Vol70, Part A, Jan 92 Water treatment in oil fields. Not referenced Production water treatment Current and emerging technologies, E & P Forum report no 2.51/176, Nov 91 Treatment of produced water State of the art, E & P Forum, Technical review No 3, Oct 82 Oil/water separation by induced air flotation, Sylvester, N.D., Byeseda, J.J., Society of Petroleum Engineers Journal, Dec 1980 Also reprinted as SPE 7886, Society of Petroleum Enqineers. Wemco Depurator system, Basset, M.G., Society of Petroleum Engineers, SPE 3349, June 1971 Extract from "Design guidelines for oil water systems", Expro EN/039, Oct 85 The effect of air distribution on the induced air flotation of fine oil in water emulsions, Van Ham, N.J.M., Behie, L.A., Svrcek,W.Y., The Canadian journal of chemical engineering, V61, Aug 1983 The removal of emulsified oil particles from water by flotation, Angelidou, C., Keskavan, E., Richardson, M.J., Jameson, G.J., Ind. Eng. Chem., Process Des. Dev., voI16, no 4, 1977 Gas flotation of produced water, Strickland. W.T., Technical progress report WRC-EP 26-75-P, Shell Oil, EP 04-7155 ASTM Standard, gives methods to determine how long a sample may be stored without significantly affecting the accuracy of the subsequent analysis. Good recent textbook discussing most aspects of emulsions in the petroleum industry Classic emulsion reference, however relatively old Detailed discussions of all aspects of emulsion technology. Ref.l.07.2.c Ref.l.OB.1.a Ref.l.08.l.b Ref.l.08.l.c
I
droplet size generated by a given mixing energy and the determination of optimum mixinq energy for coalescence. Mini version of the existing deoiling manual Discusses the theory regarding sedimentation and centrifugal processes. Discusses basic separation equipment and theory including skimmers, plate packs, skim piles, flotation Ref.2..01.2.b Ref.2.01.1 .a Ref.2.01 .l.b
lprocess for a waste water system. Does not consider droplet lsizes IPresents background theory behind oily water treatment including dropkt sizes, coalescence, flotation, Stokes law equipment etc. Investigates motion of oil and water in a tank and the effect of baffles
I I
IRef.2.Ol.l.c
IRef.2.01.1 .d
Ref.2.01.1 .e
IRef.2.01.2.a
Ref.2.01.2.c
, Ref.2.01.2.d
Ref.2.02.1 .a
,Discusses the original design and evolution of the Wemco. ]Very old reference. /Covers the Expro design guidelines for flotation units, including typical control schemes. Laboratory study investigating effect of bubble size and distribution, oil drop size and oil concentration. Discusses effect of salt water and surfactants on the flotation process. Excellent report investigating the variables affecting gas flotation. Investigates many variables including salinity, bubble size, chemicals and conducts field trials on both DGF and IGF units, Also finds gas sparging to be more efficient than a Jwemco. Discusses the Serck Baker flotation package with floating skimmers and pressure vessel design. Also mentions hybrid flotation system as desiqned for Beatrice. Modified a hydraulically induced flotation cell to dissolved gas tlotation using water from 1st stage separator as a gas saturated stream. Got significant improvement in flotation. Ordered from library, not yet reviewed
Ref.2.02.1 .b
IRef.2.02.1 .c
Ref.2.02.l.d Ref.2.02.1 .e
Advances in flotation unit design for produced water treatment, A.L. Casaday, Prepared for SPE Production Operations Symposium, Mar 21-23, 1993, SPE 25472, Mar 93 Operation and design of a hybrid flotation System, D.B. Rochford, Offshore technology conference, May 5-8,1986, paper 5247
Operating experience with the Wemco depurator for effluent water treatment in the EBP field, Marriott, K.A., 3rdmeeting on water treating and pollution abatement techniques in refineries. Paper W-6-3, 1984 Induced static gas flotation, Midway Sunset field, Pilot testing and implementation, Barnes, M.C., Carpenter, M.A., Hluza, W.L., Production Division, Oct 11, 1990 Labuan Crude Oil Terminal. Chemlink induced air flotation field test, Nov 1990, (Draft) Labuan Crude Oil Terminal, L'eau Claire induced gas floatation field test, 29th May 7th June 1991, Shah, M., EP 91-1789 Black Bayou water treating facilities, H.W. Anderson, Shell Western E & P Onshore east division, Prepared for the 1984 FacKhem. Engineering conference, Paper WAlll4, May 1984 Operating experiences with depurator units (Make: Wemco) in the Auk field, Shell Expro, EP 05-9675, Jan 83 Wemco induced gas flotation product brochures
Excellent article discussing several installations of Wemco flotation units and the operating experiences, including control schemes. Excellent discussion of a trial of the L'eau Claire Static Induced Gas Flotation system. Discusses modifications to the COntrOlS IDraft reoort of LCOT tests of Chemlink. Results very . .poor, efficiency only 15-20% Compares the Performance of a L'eau Claire and a Wemco. Better performance was obtained from the Wemco. Results for trials comparing Quadricell and Hydrocell IGF units. Hydrocell better performer and chosen for installation Covers operating experiences with Wemco type 84 in Auk field. Contains brochures, experience lists and some size and weight information for the Wemco flotation units. Contains brochures discussing the Monosep range of static induced flotation equipment, including four cell, two cell and one cell desiqns.
Ref.2.02.2.b
IRef.2.02.2.c
Ref.2.02.2.d Ref. 2.02.2.e Ref.2.02.3.a Ret2.02.4.1 Ret2.02.4.2
Bibliography
L'eau Claire aas flotation, Brochures Ekof flotation (KHD Humboldt Wedaq) Serck Baker Gas flotation brochure
Manual on the Shell parallel plate interceptor, Bataafse lnternationale Petroleum Maatschappii, MFD Oil-water separator process design, Chapter 5, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, Constructiondetails of gravity-type separators, Chapter 6, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, Rotating oil drum skimmer, Elf Antar France Extract from "Design guidelines for oil water systems", Expro EN/039, Oct 85 Separator internals for liquid-liquid or liquid-solid separation Pielkenrood systems, Teeuwen, A,, Oct 1992 Only gravity to purify produced water, Reigersman, A,, Pielkenrood, Petrochem Nr 8 (1990) Deoiling industrial waste water. Design and operation of the "CPI" (Corrugated Plate Interceptor), Report MF 81-0700, May 1981 Drainage and primary treatment facilities, Shell DEP 34.14.20.31-Gen, Oct 1992 (Draft) Evaluation of a skim tank or CPI separator alternative for effluent circa 1983 Prediction of the performance of plate pack separators Implications to design, Davies, G., Not referenced
Brochures, diagrams, proposal for unit Brochures and results from a Berlin pilot plant Informationon Serck Baker flotation, both mechanical and hydraulically induced. Also see Serck Baker equipment manual reference 9.02. Extracts from manual for the fitting of PPI plates to an API separator. Contact MFEC/24 for the oriqinal copy Discusses the application of Stokes law to sizing of API separators Discusses construction details of API separators Brochure for a oleophilic rotating drum skimmer available from Elf Antar Covers the Expro design guidelines for plate pack systems. Methods for the preliminary sizing of plate packs, written by Pielkenrood. Discusses the preference for flat plates over corrugated plates in the cross flow design Discusses the sizing, construction and operation of the Shell standard CPI Draft of updated DEP. Not yet issued. Discusses CPI installations. Gives size and cost information for evaluating skim tank and Detailed discussion predicting the outlet concentration from plate packs by considering the separation of the droplet size distribution. Discusses the sizing of plate pack on the basis of studying the droplet size distributions and predicting the actual outlet concentration for a given inlet distribution. Detailed paper discussing mechanisms of droplet coalescence on inclined plate surfaces. Note confirming MF divisions recommendations the Re is 800 for flat plates and 400 for corrugated. Short test of Fram CPI. Results good, however droplet size not known. Taken from Appendix B of report Ref 2.09.2.C Discussion on the treating of ballast water using a plate pack CPI system. Covers the various types of plate packs Covers the various types of plate packs Brochures and experience listing Plate pack coalescers and separators. Uses a unique hexagonal structure Excellent article discussing the installation and performance of hydrocyclones on the Murchison and Hutton platforms. General article describing hydrocyclones. Discusses droplet size distributions, compares with flotation. Vortoil information describing new developments including Ihe K liners, different applications (e.g. pre separation, oil dehydration and a control scheme for a centrifugal pump cyclone system Discusses the performance of progressive cavity pumps in a hydrocyclone system, control scheme given with level control valve on effluent line and pressure control on recycle. General article on Murchison/Hutton installations. Summary of some of the first hydrocyclone installations by BWN Vortoil in Australia. Discussed general principles,
Ref.2.03.1 .a
Ref.2.03.1 .b Ref.2.03.1 .c Ref.2.03.1 .d Ref.2.04.l.a Ref.2.04.l.b Ref.2.04.l.c Ref.2.04.1 .d Ref.2.04.1 .e Ref.2.04.1 .f %k04.1
.g
The design of plate separators for the separation of oil-water dispersions, Rowley, M.E.. Davies, G.A., Chem Eng Res Des, Vol. 66, July 1988 Plate separators for dispersed liquid-liquid systems: Hydrodynamic coalescence model, W. Meon, W. Rommel, E. Blass, Chemical Engineering Science, Vol48, No.1 , pp 159168,1993 Note from A. Bos, MFTB/201 Test with Fram CPI, Schoonebeek, The Netherlands, 1981. Appendix B of report Ref 2.09.2.c Tanker ballast water treating plant meets tough specs, Oil & Gas Journal, Dec 4. 1978 Skimovex brochure Nijhuis brochure RossmarWPielkenrood plate pack brochures Wemco Pacesetter plate pack Hydrocyclones: A solution to produced water treatment, Meldrum, N, Conoco, Presentedaf OTC 1987,OTC 5594. Produced water treatment with Vortoil hydrocyclones in high pressure gas production, Wolfenberger, E, (Conoco), Presented to the Houston chapter of the American filtration society, Jan 1992. Advancements in liquid hydrocyclone technology, Wafer management offshore conference, Oct 1991, Vortoil Use Of low shear pumps in conjunction with hydrocyclones for improved performance in the clean-up of low pressure produced water. Flanigan, D, (Conoco), Presentedat SPE 7989,SPE 19743, Oct 1989 Conoco's water treatment upgraded with hydrocyclones, Rosie, K, Conoco, Ocean Industry, Dec 1991/Jan 1992 Hydrocyclonesfor treating oily water: Development and field testing in Bass Strait, Presentedat OTC 7985, OTC 5079
Ref.2.04.1 .h Ref.2.04.l.i
Ref.2.05.1 .c
Ref.2.05.1 .d
?ef.2.05.1 .e 7ef.2.05.1 .f
Pqqe Bibliojiruphy-6
SlPM Droiliiig
Miiiiiiiil.
Bibliography
Collection of papers from 1980 htemational Conference on Hydrocyclones, Includes the following: 1. Determination and use of residence time distributions for two hydrocyclones, Thew, M.T., Silk, S.A., Colman, D.A. 2. Small-scale experiments on hydrocyclones for de-watering light oils. Colman, D.A., Thew, M.T., Comey, D.R. 3. Hydrocyclonesfor oil/water separation, Colman, D.A., Thew, M.T., Comey, D.R. 4. Correlation of separation results from light dispersion hydrocyclones, Colman, D.A., Thew, M.T. 5. RTD characteristics of hydrocyclones for the separation of light dispersions, Thew, M.T., Wright, C.M., Colman, D.A. 6. The effect of split ratio on heavy dispersion liquid-liquid separation in hydrocyclones, Smyth, I.C., Thew, M.T., Colman, D.A. 7. Hydrocyclone for the treatment of oil-spill emulsions, Robertson, D.S., Oswald, B.J., Colman, D.A., Thew, M.T. 8. The concept of hydrocyclones for separating light dispersions and a comparison of field data with laboratory work, Colman, D.A., Thew, M.T., Lloyd, D.D. Deoiling hydrocyclones: Separation of Forties dispersions at temperatures up to 9O"C, Nezhati, K., Thew, M., EP 90-3291, July 1988 Reduction of residual oil content in produced water at offshore gas production platform P/6A, Noort F.J. op ten, Etten, J.P., Donders, R.S., SPE 20882, Oct 1990 Low pressure hydrocyclone separator, Flanigan et al., US patent number 4,844,817, Jul4, 1989. Conoco fax, detailing claimed hydrocyclone performance for a selection o f installations Expro experience with hydrocyclones. Record of meeting with S.R. Moore of Expro, 1/2/91 Water in oil separation and produced water treatment report, Troll Olje, April 1992 Experience with Vortoils in the Murchison field, Choufoer, Norske Shell, Aug 1986 LCOT Hydrocyclone pilot tests, Mar 1980 Contains some of the foundation articles discussing the principles of hydrocyclone performance. Reference 4 in particular is the basis for the correlations presented in Appendix I. Ref.2.05.1 .g EPLIB No CD.200.033
Discusses the performance of the cyclone at a range of temperatures and droplet sizes. Discusses trials of a centrifuge, hydrocyclone and membranes for offshore gas platform. Patent application by Vortoil on the use of pumps to feed hydrocyclone systems. Discusses trials to determine the shear characteristics of different pumps and the criteria required to Qet low shear from a centrifuQe pump. Includes two cases illustrating the effect of downstream degassing vessel in reducing eflluent hydrocarbon content Discusses the Expro experience with hydrocyclones, particularly effects of sand and the use of the degassing vessel to further reduce the oil content. Discusses the proposed water treatments system for Troll Oil field, compares cyclones and centrifuges, investigates use of Chitosan for coalescence. Discusses the Murchison installation and performance. Comments on increasing the reject ratio to 30% to deal with oil contents in the order of 8%. Discusses hydrocyclone tests at Labuan, results were satisfactory, though not as high as normally expected from hydrocyclones. Use of chemicals has been proposed to improve performance. Also has graph noting a relationship between hydrocyclone outlet concentration and improvement by degassing vessel. This was roughly linear with a 10 15% reduction in effluent concentration. Results of field trials. Results favourable. Considers droplet size analysis Conoco report. Compares the performance of F and K liner Vortoils. Significant improvement with K liners. Also notes effect of corrosion inhibitor. Discusses the application of the KSLA photomicrograph technique to the hydrocyclone trials. Contains background information of droplet size distribution, grade efficiencies, cutoff diameters etc. Discusses the application of the KSLA photomicrograph technique for investigating the performance of the hydrocyclone. Discusses the use of several correlations for predicting the performance of the hydrocyclone lor different droplet size distributions. Compares the performance of hydrocyclones and centrifuges. Discusses the effect that sand has had on the Shell Expro installations. Briefly discusses the operating problems experienced with hydrocyclones to date. A collection of information describing the design, installation and commissioningof the Kittiwake pumped hydrocyclone system. Vortoil proposal for the Maui A water treatment system. Gives some interesting information such as amount of gas allowed in feed to K liners, use of strainers, reject port backflushing and limit of 30 bar pressure differential to minimise sand erosion Gives normal information expected in a specification such as scope of supply, codes and standards, inspection testinq etc. Operation guide for hydrocyclones.
Ref.2.05.l.h Ref.2.05.1 .i
Hydrocyclone field trials in Marmul, Rima and Lekhwair stations, PDO, Jan 1991 Sluis, 0. Vortoil hydrocyclone trial for Golar Nor offshore and Norske Hydro on Petrojarl 1 production ship, Troll west gas province, April 1991 North Cormorant hydrocyclone trials, Zeef, E., Visser. H.P., Nov 1987, EMTR.88.002, EP 88-2613 The performance of the Vortoil hydrocyclone for separating dispersed oil from water. An analysis of the North Cormorant Trials, Weve, D.N.M.M, Paardekooper, St., AMTR.87.004, EP 87-0572 Maui A Produced Water System, Position Paper, July 1992 Sand production, erosion and hydrocyclones, Communication to Shell Todd Oil NZ, 13/5/92 Status of Expro hydrocyclone systems, Record of telephone conversation, 10/1/91 Kittiwake produced water system. Proposed Maui produced water treatment system.
Ref.2.05.2.f Ref.2.05.2.g
Ref.2.05.2.h
Ref.2.05.2.i
Hydrocyclone specifications. Example from Vortoil of a specification for the purchase of a hydrocyclone package North cormorant hydrocyclone skid operating and troubleshooting guide, Moore, S.R., April 1990, Shell Expro Draugen hydrocyclone data sheet and package specification, Oct 1989 General arrangement diagrams for Eider Alpha hydrocyclone package, 1992 Vortoil Separation Systems, Brochure
Detailed data sheet and specification for the Draugen hydrocyclone package. Shows arrangement of hydrocyclone package A series of 7 product bulletins which give informalion on process design, control schemes and the size and weights of G and K liner packages. Also brochure from Mape, a French manufacturer of Vortoil systems.
Merpro Montassa Ltd, Brochure and information package Natco/Krebs Hydrocyclone Brochure Serck Baker hydrocyclone brochures MPE Hydroswirl hydrocyclones Design of a High-Rate, High-volume OiliWater Separator, Stires, J., Journal of Petroleum Technology, November 1982, pp 26372644 Design concepts for offshore produced water treating and disposal systems, Amold, K.E., Journal of Petroleum Technology, February 1983, pp 276-283 Evaluation of a skim tank or CPI separator alternative for effluent water treatment in the Sayala filed development, PDO Oman, circa 1983 Residence time distribution in gravity oil-water separations, Zemel, E., Bowmans, R.W., Society of Mechanical Engineers, Paper SPE 6527, Journal of Petroleum Tech, Feb 78, pp275-282 Efficient separators show good hydraulic behaviour, Bernie Zemel, Shell Development Co., Oil & Gas Journal, Dec 26,1977 Rapid filtration, Ives, K.J., Water Research, 1970, V01.4, pp201223 Art, science and filter media 2,Purchas, D.B., Filtrafion & Separation, July/Aug 1980 Filtration through deep beds, Treanor, A.I., Process Biochemistry, Sept 1971 Review of the oerformance of the Hvdromation crushed walnut filter tests in Mina al Fahal, Marmu1,'Suwaihat and Qarn Alam, Dec 1991 -July 1992, Davite, G., PDO Report BDD/159/92 Comoarison of 2 filtem.. Hvdromation and Dvnasand. Auo 1985 ,
Gives information on control system, turndown, backwashing and the setting of the reject ratio to remove massive oil contents. Brochures etc. Information on the Oilspin II hydrocyclone. Note that new hydrocyclone design expected late 1993. Also see Serck Baker equipment manual Ref.9.02 Brochures. Also see full equipment manual Ref.9.03 Design of a skim tank derived from API design principles. Also investigates the residence time distribution of flow through the vessel. Selection of articles which discuss the recommended residence time for a large volume skim tank Gives size and cost information in evaluating skim tank and Shell CPI. Discusses the residence time inside separation vessels. Found poor distribution and significant short circuiting Good article illustrating the poor residence time distributions in skim tanks and other vessels including baffled designs. Discusses general theory of deep bed filtration Discusses the characterisation methods for various types of filter media Discusses general theory of deep bed filtration Good trial of the Hvdromation filter Surnrnaw 01 Schoonebeek Hvdromation results with Fredericia Dynasaid results. Contains references to original reports As described, date not known Hydromation report into test results for treatment Of produced water in Wyoming Hydromation report into test results lor treatment of produced water Hydromation report into test results for treatment of produced water German report of BEB Hydromation tests Includes raw results Raw results from trials only Raw results from trials Only Results of InPlant trial. Generally good results with oil, though as good Discusses the range of filters used by Shell Canada and the actual installations including media filters and pre-coat filters. Quotation for Hydromation package Results of Nigerian installation Process design study examining the requirements for filtration and injection of both produced water and sea water. Extracts 01 reports only. Pretreatment stage upstream of evaporation plant WalnuVpecan shell filter Walnut shell lilter, includes informalion on use of test units. Dual media filters, also includes information on trial units Brochure Brochures and background on InPlant filters Communication from Shell Canada Not referenced Alfa Laval guide to the theory behind disk stack centrifuges. Discusses theory behind waste oil recovery, including solids removal, emulsions and the centrifuges that may be used etc. Discusses trials of centrifuge. hydrocyclones and membranes for offshore gas platform. Discusses the proposed water treatments system for Troll Oil field, compares cyclones and centrifuges, investigates use of Chitosan for coalescence. Compares the performance of hydrocyclones and centrifuges. Trial of a continuous discharging centrifuge system on some of the worst effluent streams. Results were considered good.
Ref.2.05.4.2 Ref.2.05.4.3 Ref.2.05.4.4 Ref.2.05.4.5 Ref.2.06.1 .a Ref.2.06.l.b Ref.2.06.l.c 'Ref.2.06.l.d Ref.2.06.1 .e Ref.2.07.1 .a Ref.2.07.1 .b Ref.2.07.1 .c Ref.2.07.2.a Ref.2.07.2.b Ref.2.07.2.c Ref.2.07.2.d Ref.2.07.2.e Ref.2.07.2.f Ref.2.07.2.g Ref.2.07.2.h Ref.2.07.2.i Ref.2.07.2.j Ref.2.07.2.k Ref.2.07.3.a Ref.2.07.3.b Ref.2.07.3.c Ref.2.07.3.d Ref.2.07.3.e Ref.2.07.4.1 Ref.2.07.4.2 Ref.2.07.4.3 Ref.2.07.4.4 Ref.2.07.4.5 Ref.2.07.5.a Ref.2.07.5.b Ref.2.08.1 .a Ref.2.08.1 .b Ref.2.08.1 .c Ref.2.08.2.a Ref.2.08.2.b Ref.2.08.2.c
Hydromation Deep bed filter test, North sea water filtration, Norwegian under water institute, Bergen, Norway Test results of oil and suspended solids removal from produced water in heavy crude oil production, Kozar, D, March 1980 Hydromation company deep bed filtration test. Union Oil, Grayling (Beaver creek), Michigan, 1980 Hydromation report from Shell Espana Castellon field, tanker vessel Delta Erprobung der 'Deep bed filtration" system Hydromation auf dem Betriebsqelsnde der BEB im Ruhlermoor, May 1983 Field trials with a Hydromation filter lor production water treatment, Schoonebeek oil field, Sept 84, Nam report EM/1176 Hydromation, raw results from Flotta sea water filtration trials. May 1984 Hydromation, raw results from BEB Ruhlermoor filtration trials, Jan 1984 InPlant Unit. Field trials with a Separator Filter Coalescer in Mina BDD/150/92 Filter data survey. Labuhn. I., Shell Canada, Aug 1978, EP-no. 51344 Hydromation, Quotation package for a 10,000 bpd produced water clean-up package, June 1983 Hydromation, results of Elf Aquitaine Nigeria Water injection process design study, Oil Plus Reports 4239REP-08 and 4239-REP-10, For Shell Expro PFD for Schoonebeek Hydromation deoiling filter Wemco Silver Band Brochures Hydromation brochures Serck Baker Kalsep spiral cord filters InPlant filters Summary of Shell Canada experience with a range of filters, May 90 Summary of available filtration information on Hydromation and Silver band filters. Not referenced. Theory of disk stack centrifuges lor the oil field industry, Alfa Laval product information, 1989 Waste oil recovery, Alfa Laval product information
Reduction of residual oil content in produced water at offshore gas production platlorm P/6A, Noort F.J. op ten, Etten, J.P., Donders, R.S., SPE 20882, Oct 1990 Water in oil separation and produced water treatment report, Troll Olje, April 1992 Maui A Produced Water System, Position Paper, Report92/029, July 1992 Labuan crude oil terminal, Alfa Laval disc stack centrifuges field test, Sept-Dec 1991, Shah, M
Pugc Biblicigrupli)4
SIPM Droiling Marirrrrl. EP 93-1315, Nrv 1.1, Nov 1993. File nume = 99ZZBIR.DOC
Bibliography
Centrifuge pilot test at MPNl's P/6-A platform, Donders, R.S., Perk, O.v.d., Mobil Producing Netherlands, April 1990 Produced water disposal trials by M w s k Olie og Gas, GrossPetersen, J., Jsrgensen, J. Sept 1991 Centrifuge trials on terminal emulsion and effluent water, Abraham, G., Seria, Brunei, Dec 1989 Discusses trial of centrifuge on Mobil platform. Excellent results obtained in trial Discusses results of both membrane and centrifuge trials Found the centrifuge to be successful for treatment of residual emulsions and effluent water treatment. However existing heater treaters were considered more economical to operate for emulsions and centrifuges would be too expensive for the large effluent water flow rates. Quote for centrifuges. Quote for centrifuges. Specification for disc type centrifuges, including discussions on control and interface position etc. General brochures on Alfa Lava1 centrifuges. Includes details on a centrifuge packaged into a container module. Brochures on the Leo system only Covers conventional and decantinq type centrifuges Centrifuges Discusses dissolved air and solids separation, however many of the findings and equations are relevant to deoiling. Brief background on Henry's law Use of flotation/plate pack system for a Dutch refinery Good summary of the Pielkenrood DGF units, with some sizing information and general theory. Well written and still relevant information Investigates the effect of bubble size and concentration and the coagulation/flocculationstages of DGF. Concludes chemical pre treatment is the most important step. Field trials in Brunei on hydrocarbons and solids removal Field trial of DGF in Brunei Field trial of flotation/plate pack system for produced water at Schoonebeek, The Netherlands Investigation into the poor performance of a DGF. Found fluctuating feed conditions, non-optimised use of chemicals. Investigated use of centrifuge and solvent extraction to improve performance. Brochure with size and weiqht information Brochure with size and weiqht information Brochure with size and weiqht information Brochure with size and weight information Ref.2.08.2.d Ref.2.08.2.e Ref.2.08.2.f
Budget quote for OFPX517 centrifuges, Oct 1991. Budget quote for Leo centrifuges, Oct 1991. High speed disc stack three phase centrifuges, Type OFPX-413, container modules, Alfa-Lava1 Alfa-Lava1general brochures Alfa-Lava1 Leo brochures Pieralisi brochures Westfalia brochures Dissolved air flotation for water and waste water treatment, Ward, AS., Trans IChemE, Vol70, Part B. Nov 1992 Extracts on Henry's law from Chemical Engineering Handbook, 6th ed, Perry, pp 4-60,61, 14-9, 14-15 Floc/float system cleans desalter effluent, Kleen, H., Marson, H.W., Oil& Gas Journal, Sept 8, 1980 Treatment of produced water from oil and gas production platforms by dissolved gas flotation (DGF), Reigersman, A. R O Conference, Offshore technology & environmental control on the Dutch shelf, Feb 16, 1990 Filtration, flocculation and flotation, Chapter 9, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, A conceptual model for dissolved air flotation in water treatment, Edzwald, J.K., Malley Jr, J.P., Yu, C., Water supply, Vol9, Jonkaring, pp141-150, 1991 Evaluation of induced gas and dissolved air flotation units for water treatment, Kwant, J.W.H., Informal contribution to the production technology conference, Nov 1982 Dehydration water treatment with dissolved air flotation, Nuis, D.A.E., Kwant, J.W.H, Dec 1982, Brunei. EP-no. 57250 Dissolved gas flotation, Water treatment field test on Schoonebeek produced water, Leerlooijer, K, Dec 1981, EP-no. 55594, NAM Effluentwater quality trial on AWG-1, SPC/22 Jan 1987, NAM, Report 183/86 Serck Baker DAF brochure Nijhuid Water brochure Skimovex flotation brochures RossmarWPielkenrood flotation brochures May 1993 Gas condensate water treatment using rotary hydrocyclone, Triponey, G., Woillez, J. Rotary cyclone will improve oily water treatment and reduce space requiremenVweight on offshore platforms, Gay, J.C., Triponey, G. Bezard, C., Schummer, P., Society oiPetroleum ngineers, SPE16571, Sept 1987 Dynaclean: A step fofward in produced water treatment, Bezard, C. General technical soecification. . Dvnaclean , Personal communication from Dynaclean discussing design conditions, intermittent flow configuration and effect of solids on the rotaty cyclone. A field comparison of static and dynamic hydrocyclones, Jones, P.S., SPE 20701, 1990 Dvnaclean brochures. Fax from Dynaclean listina trials and installations of the rotaw cyclone. The Serck Baker tubular precoat filter, Laboratory scale test work on bipolvmer solution Precoat filtration trials with a Serck Baker Dlant on Dunlin A, Pelgrom, J.J., Jan 1981, Shell Expro Celite Filter Aids D N Brochures
Ref.2.09.1 .c
1 Ref.2.09.1 .d
Summary of the principles behind the rotary hydrocyclone and summarises the results of the OWTC trials Discusses limits of static hydrocyclones and benefits of dynamic hydrocyclones. Includes results of test work conducted on two platforms. Gives some comparison of size and weight of units Paper from Serck Baker discussing design and sizing of Idynamic hydrocyclones 1 Information oack containina auide to the selection and specification' of a Dynacle&&clone. Very useful Fax from Serck Baker Good comparison between dynamic and 2 static cyclones. Concludes that the rotary hydrocyclone has the advantages of separating a smaller droplet size with a lower pressure drop. Dynaclean brochure with size and weiqht information. Fax from Serck Baker Test work carried out for diatomaceous earth type filter on bipolymer solution Trials with Drecoat filter. Only partially successful . . Discusses the backqround to diatomaceous earth filter media Cloth type filter, does not appear to be used in oil industry, can be used with pre-coat Tube filter suitable for pre-coat filter operations Brochure Cleanable cartridqe designed to replace disposable cartridges Etched disc cartridge type filters provide robust construction Iand absolute ratings from 3 to 40 microns (Full range of cartridge type filters, see full catalogue Ref.9.01
Ref.2.11 .I .a Ref.2.11.1 .b
IRef.2.ll.l.d Ref.2.ll.l.e Ref.2.11.1.f Ref.2.11.4.1 Ref.2.11.4.1 Ref.2.12.2.a Ref.2.12.2.b Ref.2.12.4.1 Ref.2.12.4.2 Ref.2.12.4.3 Ref.2.13.4.1 Ref.2.13.4.2 Ref.2.13.4.3
Ref.2.1l.l.c
Serck Baker tube filters, Brochure 3M Filter bags Serck Baker stainless steel cartridges Vacco metal etched disk filters Peco
I I
IRef.2.13.4.4
I I I
SlPM Deoilina Mrrrr~rol,EP 93-1315, Rrv 1.1, Niiv 199.1, File iioiiie = 99ZZRIB.DOC
Puge Biblirigruphy-9
Bibliography
Serck Baker The treatment of oily water by coalescence: Techniques and applications developed by Elf-Aquitaine, Secq, A,, Seureau, J. The treatment 01 oily water by coalescing, A. Bevis, Filtration 8 Separation, July/August 1992 Condensate cleans up oily produced water, C. Dean Cockshutt, G. Fode, Oil 8 Gas Journal, Nov 25. 1991 lnfilco Degremont, Report from trials of Colexer pilot study trials, Field 32, Lost Hills, California The SP Pack lree flow coalescer, Barnes, M.C., Shell Western E & P, Oct 1990 Coalescer evaluation for the Goodwyn A platform, Smith, P.G., Mar 89, CSIROMoodside, EP no.89-1365 Improving coalescer performance, Smith, P.G., Swift, J.D., Nov 1988, CSIROANoodside, EP no. 89-1366 Use of a mesh interceptor for water clarification, W.D. Grimes, Shell Offshore Inc, Prepared for the 1988 FacilitiesKhemical engineerinq conference, Paper TMI 2, March 1988 Skimovex lnverto coalescers Plenty Metro1general brochure Degremont (address only) Natco VFX (upflow filter/coalescer brochure) and Performax coalescer Elf Anvar brochures Monosep Spiralsep Peco Knitmesh MPE SP Pack Membrane svstems for oilv water treatment. Paoer No. 3/06 PE. Buss, G., S 5 2 KSLA, Noi92, Prepared for'the'1992 Production and process technology conference, The Hague Testing and design of ceramic membrane filters for treating of produced water, Chou, C.C.. Grimes, W.D., Schmaltz, K.S., Shell Oil, Oct 1990, prepared for the 1990 Facilities/Chemical Engineering Conference. Presentation on membrane technology, Global Engineering Production water disposal, An evaluation of membrane technologies vs. conventional treating techniques, Jan 89 Dec 89, KSLA report for PDO Oman, Vasmel, H., Schuurmans, H.J.A. Reduction of residual oil content in produced water at offshore gas production platlorm P/6A, Noort F.J. op ten, Etlen, J.P., Donders, R.S., SPE 20882, Oct 1990 OiVwater separation by membrane systems, Buss, G.Y.. Vasmel, H, Schets, T.F.M, May 90, KSLA, prepared for the 1990 SlPM Production Technology Conference Membranes for water clean-up, Callaghan, D. Feature article lor Process Bulletin, May 1990 Range of cartridge type filters, see full catalogue Ref.9.02 Discussion of coalescing theory. Also includes relerences to the Elf Anvar process Excellent article by Alan Cobham Engineering discussing the design and process variables affecting cartridge type coalescers. Discusses the use of hydraulic coalescence to improve removal of heavy oil from water by recycling condensate to water stream. Results of filter/coalescer trials Results of installing an SP Pack into a skimming tank Investigation into 5 different coalescer elements for the removal of water from condensate. Investigation into improving the performance of the water in condensate coalescer on North Rankin, Australia Improved the performance of a plate pack interceptor by installing polypropylene mesh after the plate pack to capture and coalesce small droplets. Downflow deep bed filter/coalescer Includes some general references and a filtration experience list Address and PFD for a Degremont upflow filter/coalescer Brochure Brochures on upflow and downflow Elf Anvar coalescedfilters. Also includes several trial reports and reference lists Brochure Brochures, also see Peco equipment manual, Ref.9.01. Brochures and experience Brochures, also see MPE equipment manual, Ref.9.03 Revlew of all known work on membranes for oilv water cleanup conducted within Opcos and OWTC Discussion of the successful trials and design of a full scale Alcoa membrane system to be installed on a platform for Shell Oil. Compares some of the membrane rivals Presentation by Global Engineering on all types of membranes based on work conducted for the UK Dept of Enerqy Discusses the potential application of membrane technology to water clean up. Discusses concepts of pervaporation for removal of dissolved hydrocarbons. Discusses trials of centrifuge, hydrocyclones and membranes for offshore gas platform. Summarises the results of the OWTC Phase I membrane trials and the pervaporation concept being tested by KSLA Briefly discusses various tests conducted by Mobil and NAM for membranes and oily water. Also mentions sulphate reducing membranes. Discusses current state of application of membranes for oily water clean up. Lists potential suppliers of membranes. Discusses results of OWTC membrane trials and discusses the principles behind pervaporation. Discusses the use of membranes for clean up of dispersed and dissolved oil. Ref.2.13.4.5 Ref.2.14.1 .a Ref.2.14.1 .b Ref.2.14.1 .c Ref.2.14.2.a Ret2.14.2.b Ref.2.14.2.c Ref.2.14.2.d Ref.2.14.2.e Ref.2.14.4.1 Ref.2.14.4.2 Ref.2.14.4.3 Ref.2.14.4.4 Ref.2.14.4.5 Ref.2.14.4.6 Ref.2.14.4.7 Ref.2.14.4.8 Ref .2.14.4.9 Ref.2.15.l.a Ref.2.15.l.b
Ref.2.15.l.c Ref.2.15.1 .d
Recent advances in the application of membrane technology for the removal of oil and suspended solids from produced waters, Zaidi, A., Simms, K., Kik, S. Nelson, R., International Produced Water Symposium Feb 4-7, 1992, San Diego OiVwater separation by membrane systems, Buss, G.Y.. Vasmel, H., Schets, T.F.M., ST/1, KSLA, 3 May 90, Prepared for 1990 SlPM Production Technology Conference, Paper 3P/05 Production water disposal, An evaluation of membrane technolooies vs. conventional treatina techniaues. . . Vasmel. H.. Schets, f.F.M., 1989, Draft Reverse osmosis and ultrafiltrationsolve seoaration Droblems. ' Gooding, C.H., Chemical Engineering, Jan 7 1985 Treatment and disposal of waste waters produced with coalbed methane by reverse osmosis, Simmons, B.F., Produced Water, Ray, J.P., Engelhart, F.R., Plenum Press, 1992, pg 593 Removal of oil, grease and suspended solids from produced water with ceramic crossflow microfiltration, Chen, A.S.C., Flynn, J.T., Cook, R.G.. Casadav. A.L., SPE Production Engineerina,
I .
Ref.2.15.1 .i Ref.2.15.l.j
considerations. Indirectly useful Discusses the application of reverse osmosis for oily water cleanup. Claims in some cases technique can be technically and economically feasible. Discussions 01 the olfshore trials of the Alcoa Petrolux system. Also see 2.15.1 .b
IRef.2.15.1 .k
Ref.2.15.1.l Ref.2.15.l.m
Oil and suspended solids removal from produced water using ultrafiltrationand microfiltration, Zaidi, S. Kok, K. Simms, J Schmidt, Wastewater Technology Centre. Burlington, Canada Preliminary ultrafiltrationexperiments on formation water from oil platforms, Idema, W., Stork membranes, Jan 89 Membraanfiltratieproevenop oliehoudend formatiewater, Nov 1990, NAM Report 18703, Dutch language (Results of Stork membrane trials at Schoonebeek) Produced water disposal trials by Marsk Olie og Gas, GrossPetersen, J., Jsrgensen, J. Sept 1991 Review of the execution of the membrane test carried out on K7FA-1 between 30/3/92 and 1/6/92, from SEFI15, NAM
Good article summarising the experience of a range of membrane trials in Canada and the US. Lists a range of membrane manufacturers. Investigates the suitability of Stork ultra filtration membranes applied at pilot plant level for filtration of oily water. Results of Stork membrane trials conducted at Schoonebeek to select the best membrane IOapply to produced water. Discusses results of both membrane and centrifuges trials Discusses the problems experienced in conducting an oflshore membrane trial utilisinq the Hoogovens membrane.
fuge Bib/iogrup/~y 10
SlPM Deoiling Mcinuul, EP 93-1315. Rev 1.1. Nov 1993. File nume = 99ZZBIB.DOC
Bibliography
Ultrafiltration field pilot testing for the treatment of produced water, (Zenon membranes) Volume I and 11, June 1990, EP 90-3729 The trial of an SDI membrane unit on Expro's lnde Julliet between 23 April and 22 June 1993, G. Buss (KSLA), B Touw (Expro, Lowestoft), G. van Hirtum (KSLA), Draft report Detailed report on field trials at the Shell Canada Peace River development for use of a Zenon ultrafiltration membrane for treatment of produced water from a steam stimulated heavy oil reservoir. Found gradual fouling by clays over time and could not establish a constant flux rate. Draft report of a trial of the SDI membrane with dispersed and dissolved hydrocarbons. Good results with dispersed hydrocarbons, but could not remove all dissolved
Stripping of dispersed hydrocarbons from water, Visser, R.M., van Huuksloot, A., Visser, H.P., EE.4 KSLA, 20 Sept 1991 (See Ref.3.02.2.b) Drying of natural gas condensates by stripping with dried gas, Part I, Sizing of the stripper column lor the NAM-F3 project, J.A.M. Spaninks, A.E. Cornelissen, KSLA AMER.82.052, EP 056091 Drying of natural gas condensates by stripping with dried gas, Part II, Model experiments, A.E. Cornelissen, H.P. Visser. KSLA AMER.83.037, EP 05-9146 Drying of natural gas condensate by stripping with dried gas, Part Ill.A tray-to-tray computer program lor stripper column design, A.E. Cornelissen, KSLA AMGR.83.211, EP-59207.
drocarbons could not be removed. Suoersedes reDort def.3.02.2.c Investigates stripping of dispersed hydrocarbons from water. Superseded by report Ref.3.02.2.b First report discussing the mass transfer mechanisms for a condensate stripper. Gives an example calculation for estimating the water removal rate at 50% and 90% removal of water. The theory and models proposed in Part I (EP 05-6091) are developed further and tested in laboratory trials. Measured stripping rate was found to be faster than predicted by model. Discusses the computer program COLUMN used to calculate stripping performance of a condensate dehydrator using dry gas stripping. Program allows user to determine required number of trays. Gives listing of program (Fortran) and discussion of theory behind program. Program based on results from Pari I (AMER.82.052) and Part 11 (AMER.83.037) Results of condensate stripping experiments conducted on the NAM-fb-1 platform using a packed column.
Ref.3.02.2.c Ref.3.02.2.d
Ref.3.02.2.e Ref.3.02.2.f
Drying of natural gas condensate by stripping with dried gas Field experiments on the NAM K-15-fb-1 platform, KSLA AMER.84.036
Ref.3.02.2.g
iwiiw
= 99ZZlllR.DOC
PuRe Biblio#ruphy-l I
Drying of natural gas condensate by stripping with dried gas Further field experiments on the NAM K-15-fb-1 platform, KSLA AMER.86.028 Bio-reclamation of oil field produced waste waters: Characterisation and feasibility study, Tellez, G.T., Nirmalakhandan, N., lntemational Produced Water Symposium Feb 4-7, 1992, San Diego Design of aerobic treatment units, Ramalho, R.S., Hydrocarbon processing, Part 1 and 2, Oct and Nov 1979 Removing VOCs from contaminated water: Part 1, Heilshorn, E.D., Chemical Engineering, March 1991 Oily effluent treatment by the BP Effluent treatment process, Oldham, G.F.. Sept 1979, EP 53584 Reduce oil and grease content in waste water, Capps, R.W.. Matelli, G.N., Bradford, M.L., Hydrocarbon Processing, June 1993 Evaluation of soluble oil and grease removal mechanisms in refinery wastewater treatment systems, P.T. Sun, R. van Compemolle, G.R. Mueller, J.J. Gentempo, Technical progress report WRC 122-86, MF 87-0254, Feb 87 The use of innovative biological reactors in the treatment of ground water contaminated with intermediate levels of aromatics, P.T. Sun, C.L. Price, G.W. Edmunds, Technical progress report WAC 4-87, MF 87-0863, July 87 Removing VOCs from contaminated water: Part 1, Heilshom, E.D.. Chemical Engineering, March 1991 Remove organics by activated carbon adsorption, Stenzel, M.H., Chemical Enqineering Practice, April 93 A fresh look at liquid-liquidextraction, Part 1: Extraction systems, Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Feb 1991 A fresh look at liquid-liquid extraction, Part 2: Inside the Extractor, Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Feb 1991 A fresh look at liquid-liquidextraction, Part 3: Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Apr 1991 Removal of hydrocarbons from effluent water, Equilibrium and kinetic measurements, Visser, H.P., Heexen. R., EW4, KSLA, 19 Oct 1990 Removal of dissolved hydrocarbons from effluent water using extraction, Jan -July 1992, Visser. H.P., Heezen, R., KSLA AMGR.90.285 Cooling water clean up by ozone, Echols, J.T., Mayne, S.T., Chemical engineering, May 1990 Waste water treatment by ozone oxidation, Berre Refinery, 1975 Looking to treat wastewater? Try ozone. Lin, S.H., Yeh, K.L., Chemical Engineering, May 1993 Investigations into the use of modified zeolites for removing benzene, toluene and xylene from saline produced waters, Janks, J.S., Cadena, F., International Produced Water Symposium Feb 4-7, 1992, San Diego OiVwater separation by membrane systems, Buss, G.Y., Vasmel, H, Schets, T.F.M, May 90, KSLA, prepared for the 1990 SlPM Production Technology Conference Treatment of produced water, Phase A, OLF report, May 1992 Peco (Perry Equipment Corporation) Filtration/Separation division, Equipment Manual Serck Baker, Fluid processing technology, Equipment Manual
Additional stripping experiments using trays instead of packing in the column. Discusses the acclimatisation of micro-organisms for the biological treatment of saline production waters Discusses a range of aerobic treatment configurations and desiqn requirements Discusses general requirements for activated carbon adsorption and biological treatment systems Published BP paper discussing the selection of a effluent treatment system comprising media filters as a pre treatment followed by percolating filters for biological treatment. Discusses oily water treatment from the perspective of improving the performance of downstream biological treatment systems Discusses the breakdown of waste water from the Matinez manufacturing complex, particulady the presence of napthetic acids. Found that low molecular weight acids were biodegradable and higher MW acids could be absorbed onto activated carbon. Laboratory trials to investigate a Sludge Blanket Biological Reactor (SSBR), Aggregated Biological Solids Reactor (ABSR) and a Fluidised Bed Biofilm Reactor (FBBR) fro removal 10 mgA BTEX compounds. ABSR and FBBR recommended for pilot trials. Conceptual design proposed for a Aerated Biological Carbon Bed (ABCB). Discusses general requirements for activated carbon adsorption and biological treatment systems Discusses general requirements for activated carbon adsorption systems Discusses mass transfer theory behind liquid-liquid extraction systems Discusses the types of equipment behind liquid-liquid extraction systems Discusses pilot trials and scale up. Investigates liquid-liquid extraction of aromatics from water Discusses the results of experiments investigation a two stage extraction process. Discusses variables affecting the performance of the system. Although more orientated for controlling microbial growth, has some useful information on ozone systems. Discusses use of ozone alone for the removal of organics from water. Good results on phenols, BOD and COD reduction poor. Discusses the uses for ozone, including oxidation of organics and inorganics, as an alternative to chlorine. Discusses the methods for ozone generation and methods for effective dosing and use. Discusses background and use of modified zeolites on test waters and produced waters. Technology at a very early stage of development Summarises the results of the OWTC Phase 1 membrane trials and the pervaporation concept being tested by KSLA Extract of report discussing the various methods of dealing with heaw metals. Estimates equipment sizes for offshore . . installation. Includes equipment for liquid filtration, gas filtration/ separation, gas scrubbers, liquid phase separation, filter elements. Includes information on coarse filters, media filters, deaerators, reverse osmosis, ion exchange, static and rotary hydrocyclones, plate separators, dissolved gas flotation, chemical injection Includes information on oil/water skimmers, SP Packs, plate packs, hydrocyclones, flotation, caisson designs. Tested performance of Vortoil static cyclone, Dynaclean rotary cyclone and Wemco flotation cell. Tested performance of Vortoil static cyclone, Dynaclean rotary cyclone and Alfa Laval centrifuge. Significant problems with commissioning instruments. Trials not rigorously applied. Superseded by Phase II trials. Tested four membranes. See section 8.17 for more information
Ref.3.02.2.h Ref.3.03.1 .a
Ref.3.03.1 .g
Ref.3.M.l.a
I Ref.3.05.1 .a
Ref.3.05.1 .b Ref.3.05.1 .c Ref.3.05.2.a Ref.3.05.2.b Ref.3.99.1 .a Ref.3.99.l.b Ref.3.99.1 .c
Ref.3.M.1 .b
Ref.3.99.2
MPE, Modular production equipment, Equipment Manual Final report on the hydrocyclone/lGF trials conducted as the Orkney Water Test Centre, Nov 1988-Oct 1989. Tulloch, S.J., Jan 1990, EP-No.90-2641 Dynaclean and Vortoil hydrocyclones and Alfa Laval 3 phase disc stack centrifuge trials with condensate water mixes at Orkney Water Test Centre, Jan March 1987, Nezhati, K., May 1990, EP. N O 90-3599 Final report on the oil-in-water monitor testing conducted at Orkney Water Test Centre, February 1989 to October 1989, Tullock, S.J., March 1990, EP-No.90-3673 Membrane filter trials with various oily waters at Orkney Water Test Centre, Phase I, Nezhati, K., April 1991, EP-No.91-1017
Ref.9.03 Ref. OWTC EP 90-2641 Ref.OWTC EP 90-3599 Ref.OWTC EP 90-3673 Ref.OWTC EP 91-1017
Puge BiDliogruphy-I2
SlPM Deoilinx Mmrtirl. EP 93-1315, Rrv 1.1, Nov 1993, File ncrrnr = 99ZZBIB.DOC
Oil in water trials conducted at the Orkney Water Test Centre, Phase II, November 1990 to March 1991, Tullock, S.J., Oct 1991, EP-N0.91-2151 Membrane filter trials with various oily waters at Orkney Water Test Centre, Phase 11, Nezhati, K., Sept 1991, EP-No.91-2152 Testing of coalescing devices to enhance the performance of hydrocyclones at Orkney Water Test Centre, Webster, J.D., March 1992, EP-No.92-0942 Comparative testing of new generation deoiling hydrocyclones by Orkney Water Test Centre, Tulloch, S.J., Aug 1992, EP 92-1900 Sulphate removal membrane filter trials, EP-No. 92-1905 Particle size analyser trials conducted at the Orkney Water Test Centre November 1990 February 1991, Tullock, S.J., Oct 1992, EP-N0.92-1952 Comparative testing 01 new generation deoiling hydrocyclones, Part 11, May 1993, EP. No. 93-1492
Performance of monitors improved. Variables investigated more rigorously Tested three membranes plus the Wemco Silver band litter. See section 8.17 for more inlormation on membranes. Wemco performance considered good. Investigates a range of coalescers including Knitmesh Dusec, Spiralsep, SP Pack, Sulzer Mellapak structured packing, and coalescing hydrocyclones. An appendum investigated the combined performance of coalescers and hydrocyclones, results were not as good as anticipated. Compared performance 01 Vortoil F liner Krebs, Hydropak and Hvdroswirl Investigates use of membranes lor sulphate removal from sea water. Compares a range of particle size analysers. Galai emerges as a strong contender having good performance and image analysis capabilities and can operate at process conditions. Compares performance of Vortoil F, G and K liners. Finds performance similar at high flows, large droplets, however K liner is superior for small droplets and low pressure drop Identified 34 different oil-in-water monitors from 19 vendors. Includes summaries of the operating method and range lor each instrument
Rel.OWTC EP 92-1900 Ref.OWTC EP 92-1905 Ref.OWTC EP 92-1952 Ref.OWTC EP 93-1492 Rel.OWTC EP not assiqned
Further developments in oil-in-water monitor technology Phase II. Monitor selection, Desk study report", Tullock, S.J., June 1993
SlPM Deotltng M(mrrcr/, EP 93-1315. Rev I I . Nov 1993, Frk tririlre = 99ZZBlB DOC
Puge Biblingruphy-I3
Bibliography
Puxc Bibliojiruphy- 14
SIPM Deniliiih. M~rrivirl, &I 93.1315, Rev 1.I , Nov 1993. F#e ncinrr = 99ZZBlB.DOC