PROCESS SIMULATION REFINERY PROCESSES SAMPLER

Modelling and Optimization

John E. Edwards
Process Simulation Engineer, P & I Design Ltd

First Edition, June 2013 P&I Design Ltd

Released by P & I Design Ltd 2 Reed Street, Thornaby TS17 7AF www.pidesign.co.uk Private distribution only Copyright P & I Design Ltd 2012 jee@pidesign.co.uk Printed by Billingham Press Ltd, Billingham TS23 1LF

Process Simulation Refinery Processes Contents

Section 1 Section 2 Section 3 Section 4 Section 5 Section 6 Section 7 Section 8 Section 9 Section 10 Refinery Processes Thermodynamics Crude Column Vacuum Still Splitting and Product Purification Hydrotreater Catalytic Reformer Amine Treatment Miscellaneous Applications General Engineering Data Section End 5 9 13 23 27 43 47 53 57 59 70

Preface
The process industry covers a broad spectrum of activities that involve the handling and treatment of gases, liquids and solids over a wide range of physical and processing conditions. This manual provides a comprehensive review of the fundamentals, definitions and engineering principles for the study of processes encountered in hydrocarbon processing using steady state simulation techniques. Applications are presented for a wide range of processing units involving design and operations. Process simulations are carried out using CHEMCAD software by Chemstations, Inc. of Houston. This manual has been developed with the full support of Chemstations simulation engineers based in Houston. The simulation of crude distillation at atmospheric pressure, vacuum distillation and sour gas amine treatment is covered in Section 13 Process Measurement and Control of the book Chemical Engineering in Practice by J.E.Edwards. This manual includes these topics and extends the study to other refinery processes including splitters, stabilizers, hydrotreaters and reformers. Thermodynamics are reviewed with special reference to the application of pseudocomponent curves and crude oil databases Each topic is in the form of a condensed refresher and provides useful practical information and data. Each section is numbered uniquely for contents and references, with the nomenclature being section specific. The references are not a comprehensive list and apologies for unintended omissions. Reference is made to many classic texts, industry standards and manufacturers data. Information has been mined from individual project reports and technical papers and contributions by specialists working in the field.

The Author
http://uk.linkedin.com/pub/john-edwards/1b/374/924
John E.Edwards is the Process Simulation Specialist at P&I Design Ltd based in Teesside, UK. In 1978 he formed P&I Design Ltd to provide a service to the Process and Instrumentation fields. He has over fifty years experience gained whilst working in the process, instrumentation and control system fields.

Acknowledgements
A special thanks to my colleagues at Chemstations, Houston, who have always given support in my process simulation work and the preparation of the articles that make up this book: N.Massey, Ming der Lu, S.Brown, D.Hill, A.Herrick, F.Justice and W.Schmidt of Germany Also thanks to my associate P.Baines of Tekna Ltd for help with the organic chemistry topics.

Section 1 Refinery Processes

References 1. 2. 3. 4. Shrieve, Chemical Process Industries, Chapter 37, 5th Edition, McGraw Hill, 1984. J.A.Moulijn, M.Makkee, A.Van Diepen, Chemical Process Technology, Wiley, 2001. G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000. W.L.Nelson, Petroleum Refinery Engineering, 4th Edition, McGraw Hill, 1958.

Overview Most refinery products are mixtures separated on the basis of boiling point ranges. The block diagram, by API, shows overall relationship between the refining processes and refined products.

Refining is a mature, complex and highly integrated operation. Columns with a wide variety of internals are used in many stages of the process. Fractional distillation under vacuum and pressure conditions is used to separate components. Light ends are steam stripped and the heavy ends are vacuum distilled at reduced the temperatures. Stabilizers are used to remove light ends, including LPG, to reduce the vapor pressure for storage and subsequent processes. Absorbers and strippers are used to remove unwanted components such as sulphur. Simple distillation processes do not produce sufficient gasoline above the minimum required octane number. This is achieved by converting heavy to light hydrocarbons using catalytic processes including fluidic catalytic cracking (FCC), hydrotreating, hydrocracking, catalytic reforming and alkylation.

Crude petroleum consists of thousands of chemical species. The main species are hydrocarbons but there can be significant amounts of compounds containing sulphur (0-6%), oxygen (0-3.5%) and nitrogen (0-0.6%). The main groups are: Aliphatic or open chain hydrocarbons as detailed in the table: Aliphatic or open chain hydrocarbons (hc) Properties Class Formula saturated hc, unreactive paraffins CnH2n+2 unsaturated hc, forms olefines CnH2n additive compounds acetylenes CnH2n-2 reactive, OH replaced alcohols, phenols RCH3OH additive compounds ketones RR1.CO

Descriptor -ane -ene -ol -one

Member C2H6 ethane C2H4 ethylene C2H2 acetylene C2H5OH ethyl alcohol (CH3)2.CO acetone

n-paraffin series or alkanes (CnH2n+2) This series has the highest concentration of isomers in any carbon number range but only occupy 20-25% of that range and make low octane gasoline. Most straight run (distilled directly from the crude) gasolines are predominately n-paraffins. The light ends primarily consist of propane (C3H8), n-butane (C4H10) together with water which are defined as pure components. iso-paraffin series or iso-alkanes (CnH2n+2) i-butane (C4H10) is present in the light ends but these compounds are mainly formed by catalytic reforming, alkylation or polymerization. olefine or alkene series (CnH2n) This series is generally absent from crudes and are formed by cracking (making smaller molecules from larger molecules). They tend to polymerize and oxidize making them useful in forming ethylene, propylene and butylene. Ring compounds Naphthene series or cycloalkanes (CnH2n) These compounds are the second most abundant series of compounds in most crudes. The lower members of this group are good fuels and the higher members are predominant in gas oil and lubricating oils separated from all types of crude. Aromatic series Only small amounts of this series occur in most common crudes but have high antiknock value and stability. Many aromatics are formed by refining processes including benzene, toluene, ethyl benzene and xylene. Lesser Components Sulfur has several undesirable effects including its poisonous properties, objectionable odour, corrosion, and air pollution. Sulfur compounds are removed and frequently recovered as elemental sulfur in the Klaus process. Nitrogen compounds cause fewer problems and are frequently ignored. Trace metals including Fe, Mo, Na, Ni and V are strong catalyst poisons and cause problems with the catalytic cracking and finishing processes and methods are used to eliminate them. Salt, which is present normally as an emulsion in most crudes, is removed to prevent corrosion. Mechanical or electrical desalting is preliminary to most crude processing. Crude oil is classified on the basis of density as follows: Light less than 870 kg/m3 >31.1 API Medium 870 to 920 kg/m3 31.1 API to 22.3 API Heavy 920 to 1000 kg/m3 22.3 API to 10 API Extra-heavy greater than 1000 kg/m3 <10 API Bitumen Heavy or extra-heavy crude oils, as defined by the density ranges given, but with viscosities greater than 10000 mPa.s measured at original temperature in the reservoir and atmospheric pressure, on a gas-free basis
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Natural Gas Light hydrocarbon mixture that exists in the gaseous phase or in solution in crude oil in reservoirs but are gaseous at atmospheric conditions. Natural gas may contain sulphur or other nonhydrocarbon compounds. Natural Gas Liquids Hydrocarbon components recovered from natural gas as liquids including ethane, propane, butanes, pentanes plus, condensate and small quantities of non- hydrocarbons. Atmospheric and vacuum distillations produce the different fractions as detailed in the table below.
Crude Petroleum Fractional Distillation 40-70 C 70-120C 120-150 C 150-300 C Gas oil
0.65

Temperature Description Density Composition

<30C Gaseous Hydrocarbon

>350 C Heavy oils

Naptha
0.72

Benzene
0.76

Kerosene
0.8

Residue Asphalt or Bitumen

C3H8, C4H10

C5H12, C6H14

C6H14, C7H16 C8H18

C8H18, C9H20

C10H22, C11H24 C12H26 to C18H36

C18H38 to C28H58 Roads, Wax paper

Applications

Gas fuel or enrichment

General Solvent Solvent for Home solvent, for oils, oils, fats & heating aviation fats & varnishes Jet fuel spirit varnishes Gasoline, contains C6H14, C7H16, C8H18 40-180 C

Diesel, fuel oils

Further fractionation of the 70 to 150C cut is required to obtain the naptha and benzene cuts. Vacuum distillation of the topped crude is required to obtain Light Vacuum Gas Oil (LGVO) and Heavy Vacuum Gas Oil (HVGO) When the difference in volatility between components is small a solvent of low volatility is added to depress the volatility of one of the components. This process is known as extractive distillation. Butenes are separated from butanes using this method with furfural as the extractant. When a high volatility entrainer is used the process is known as azeotropic distillation. Anhydrous alcohol is formed from 95% aqueous solution using benzene to free the azeotrope and high purity toluene is separated using methyl ethyl ketone as the entrainer. Typical Crude Oil Products Profile Ref EIA March 2004 Data Product Refined gallons/barrel (gal/bbl) Gasoline 19.3 Distillate Fuel Oil (Inc. Home Heating and Diesel Fuel) 9.83 Kerosene Type Jet Fuel 4.24 Residual Fuel Oil 2.10 Petroleum Coke 2.10 Liquified Refinery Gases 1.89 Still Gas 1.81 Asphalt and Road Oil 1.13 Petrochemical Feed Supplies 0.97 Lubricants 0.46 Kerosene 0.21 Waxes 0.04 Aviation Fuel 0.04 Other Products 0.34

RON 90 STANDARD 10% n heptane C7H16 straight chain hydrocarbon 90% iso octane C8H18 branched chain hydrocarbon (ALSO KNOWN AS 2,2,4 TRIMETHYL PENTANE) Gasolines are compared to this mixture in relation to deflagration performance under pressure in a test engine

crude oil dist Catalytic cracking and other methods Fluid Catalytic Cracking FCC and other methods Gasoline light naptha heavy naptha

Refinery Process Summary:

dist

light gasses Naptha (full range) kerosenes Diesels Other high boilers

<30c >30 <200 >150<270 >180<315

deg c >35 <145 >140 <205

straight chain alkanes cyclic alkanes benzene ring structures C10H22 Decane (paraffin) method 1 C12H26 Dodecane (paraffin) method 1 C6H12 Cyclohexane (napthene) method 2 C8H16 Ethyl Cyclohexane (napthene) method 2 CH3 C2H5 C6H6 ethyl benzene (aromatic) 4H2 Hydrogen CH3 CH3 C6H6 Dimethyl benzene (aromatic) 3H2 Hydrogen iso octane Ethene iso octane Butene Benzene Hydrogen Ethyl Benzene

Heavy Naptha eg Mutineer (Aus) Paraffins Napthenes Aromatics vol% 62 32 6

Gasoline (500 components) iso octane Cyclopentane Ethyl Benzene

% vol? 50 technically 2,2,4 trimethyl pentane 30 20 C8H18 C2H4 C8H18 C4H8 C6H6 3H2 C6H6 C2H5 2.5 H2

8
method 3 Iso octane Methane C8H18 CH4 Dimethyl cyclohexane C8H18 method 3

Section 2 Thermodynamics
References 1. G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000 2. American Society for Testing and Materials (ASTM International), Standards Library Global K and H Models The following table gives a summary of suitable K and H models for common refinery processes. Refinery Processing Thermodynamic Models Summary Process K Model H Model (Forced) Crude Atmospheric Distillation Grayson Streed Lee Kessler Vacuum Distillation ESSO Lee Kessler Hydrotreater SRK SRK Sour Gas Treatment Amine Amine FCC Gas Treatment Peng Robinson Peng Robinson Propylene Splitter Peng Robinson Peng Robinson Compression BWRS BWRS Grayson Streed K model is primarily applicable to systems of non-polar hydrocarbons. It is good for modelling hydrocarbon units, depropanizers, debutanizers, or reformer systems. The approximate range of applicability is as follows: Temperature Range 0 to 800F -18 to 430C Pressure Range < 3000 psia < 20000 kPa

ESSO K model predicts K-values for heavy hydrocarbon materials at pressures below 100 psia. The average error for pure hydrocarbons is 8% for p* > 1 mmHg, and 30% for p* between 10E-06 and 1 mmHg according to API Technical Data Book Vol 1. It is good for modelling vacuum towers. Lee Kessler H model is good for hydrocarbon systems. AMINE K model is based on the Kent Eisenberg method to model the reactions with diethanolamine (DEA), monoethanolamine (MEA), methyl diethanolamine (MDEA) being included. The chemical reactions in the CO2-Amine system are described by the following reactions: RR'NH2+ RR'NCOO + H2O CO2 + H2O HCO3H2O H+ RR'NH HCO3CO3- H+ + RR'NH + HCO3 + H+ + H+ + OH-

Where R and R' represent alcohol groups. The reaction equations are solved simultaneously to obtain the free concentration of CO2. The partial pressure of CO2 is calculated by the Henry's constants and free concentration in the liquid phase. The AMINE K Model in CHEMCAD treats the absorption of CO2 in aqueous MEA as a fast chemical reaction, in other words, gas film controlled implying a very low stripping factor. However it is known that this process is liquid film controlled since Henrys Law controls the diffusion of CO2 into the liquid prior to chemical reaction taking place.

Section 3 Crude Column

Case/File Name R3.01 Crude Column Simulations Description Crude Column Feed References 1. H.Kister, Distillation Design, McGraw-Hill, ISBN 0-07-034909-6 2. G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000 3. W.L.Nelson, Petroleum Refinery Engineering, 4th Edition, McGraw Hill, 1958 Process Description The simplified process flow diagram shows the basic layout for the crude and vacuum distillation units.

Desalted crude is preheated with the pump around and topped crude heat exchangers prior to being heated to ~620F in the direct fired furnace. Above this temperature thermal decomposition (cracking) will take place resulting in increased light ends and fouling of heat exchange surfaces due to carbon based deposits. The following initial guidelines are suggested: 1. 2. 3. For paraffin based crudes at moderate furnace temperatures, an estimated cracked gas rate of 5.0 SCF/bbl (42 gal/bbl) crude oil is reasonable. For asphalt based crude oil a cracked gas production of 2.5 SCF/bbl crude oil is suggested. The cracked gas may be given an arbitrary composition as follows: 50 mol% methane, 40 mole% ethane, and 10 mole% propane.

The feed to the atmospheric crude tower is a mixed vapor-liquid phase of ~0.4 vapor fraction. The vapours flow upwards and are fractionated to yield the products. Crude towers are typically 4m diameter, 2030m in height with 1530 trays.
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A typical Process Flow Diagram for a crude unit, including pump-around circuits and side strippers, is shown. The column is modelled on the basis of theoretical stages, as opposed to actual trays, so it is necessary to apply tray efficiency to translate the actual trays NA to theoretical trays NT where =NT/NA. Note that commercial simulators provide various tray efficiency models, which are not suitable for crude distillation columns. Tray efficiency should be based on experience. The relationships between NA and NT are indicated in the diagram.

The liquid product sidestreams contain light hydrocarbons which must be removed to meet the initial boiling point specification for the products. The liquid sidestreams are fed to strippers that use either a reboiler or steam to strip out these light components which are returned to the crude tower. Current preference is to use reboiled side strippers for the lower boiling products to reduce the heat load on the crude tower condenser and the sour water stripper. Side strippers are typically 1-2m diameter, 3m in height with 48 trays representing 23 theoretical stages. Height limitations can be met by using structured packing which has high capacity and low HETP values as compared to trays. Pumparound cooling circuits provide reflux to remove the latent heat from hot flash zone vapors and condense the side products. A pump-around zone may be considered equivalent to an equilibrium flash where equilibrium liquid is recirculated. The large flow of pump-around liquid creates a region of constant liquid composition that eliminates fractionation. The heat removed preheats the crude feed.

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Section 4 Vacuum Still

Case/File Name R4.01 Vacuum Still Simulations Description Vacuum Unit

Vacuum distillation is used to separate the high boiling bottoms from the crude column. The Vacuum Unit process flow diagram is shown with distillation UnitOp 1 selected as Tower+.

The thermodynamic selection is K Model ESSO and H Model Lee Kessler. The feed is defined by the following specification: Feed rate 360 m3/day Bulk gravity 0.9168 specific gravity Feed temperature 150F Feed pressure 58 psia Distillation curve volume % based on TBP at 1 atm

12

The column specifications are: Vacuum Column Data Description Specification Number of strippers 0 Number of pumparounds 2 Number of exchangers 1 Number of side products 2 Stages Theoretical 8 Feed 8 Column pressures Top 30 mmHg dP 35 mmHg Stripping Steam condition 335F and 115 psia Bottom steam flow 166.67 lb mol/h Condenser Total Reboiler None Pumparound 1 Stages Draw-3 Return-1 Flow 276218 kg/h Phase liquid Duty 0 MJ/h Pumparound 2 Stages Draw-5 Return-4 Flow 538139 kg/h Phase liquid Duty 0 MJ/h Side Product Draw 1 Stage 3 Flow 72 m3/h Phase liquid Side Product Draw 2 Stage 5 Flow 213 m3/h Phase liquid Side Heat Exchanger Stage 8 No duty (Feed stage) Stage Specifications Stage 3 1 kmol/h Liquid flow Stage 5 85 m3/h Liquid Flow Stage 8 69 m3/h Liquid Flow

Pseudocomponent Curves allow group plots to be generated for the streams:

13

Section 5 Splitting and Product Purification

Case/File Name R5.01 R5.02 R5.03 R5.04 R5.05 R5.06 R5.07 Splitting and Product Purification Simulations Description Deethanizer Debutanizer Depropanizer Debutanizer Reflux Depropanizer C3 Splitter C4 Splitter C4 Splitter Tray Column Kerosene Splitter

1. 2. 3. 4.

References H.Kister, Distillation Design, McGraw-Hill, ISBN 0-07-034909-6 G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000 G.L.Kaes, Practical Guide to Steady State Modelling of Petroleum Processes H.Kazemi Esfeh and I.Aalipour mohammadi, Simulation and Optimization of Deethanizer Tower, 2011 International Conference on Chemistry and Chemical Process, Singapore

Introduction A primary activity in hydrocarbon processing involves the fractionation and purification of light ends using columns, the most common being stabilizers, deethanizers, debutanizers and depropanizers. A typical purification plant schematic is shown:

Deethanizer The deethanizer removes ethane (C2H6) and lighter components which may be fed to the olefines unit for production of ethylene (C2H4) or polyethylene or polypropylene products. Bottoms are fed to the debutanizer. Design for C2 mole fraction or C2/C3 mole ratio in the bottoms. Debutanizer The debutanizer separates mixed LPG product (mostly C3s and C4s) and a stabilized condensate (C5+). Design for RVP in bottoms with 12 psia being typical and reflux ratio 0.5 1.0 Depropanizer The depropanizer separates propane (C3s) as overheads from the butane (C4) to the bottoms. Stabilizer Stabilizers are used to remove light ends (mainly C4s) from condensate to meet Reed Vapour Pressure (RVP) specification for future processing or to allow storage in floating roof tanks. Design for RVP in bottoms with 12 psia being a typical maximum value All purification units use the bottom tray or reboiler temperature and reflux for control. The stabilizer uses bottom tray or reboiler temperature alone as there is no condenser for reflux control. Using these parameters in process simulation allows predicted product properties to be compared against actual process conditions. Simulation parameters can be adjusted to match current behaviour to provide a powerful troubleshooting tool.
14

Splitters are used extensively in hydrocarbon processing, including C2s, C3s, C4s and Naphtha. The process simulation methods used are similar to those for the purification process with the CHEMCAD SCDS UnitOp being used. Tray Column Industry Practice and Efficiencies (1) Actual Trays Overall Efficiency 25 - 35 70 - 75 110 - 130 95 - 100 200 - 250 95 - 100 70 - 80 85 - 90

Process Naphtha Splitter C2 Splitter C3 Splitter C4 Splitter C2 Splitter (C2H6 C2H4)

Theoretical Trays 18 - 25 105 - 125 190 - 240 60 - 68

This involves the separation of ethylene from ethane using low temperature distillation. The splitter is normally operated at high-pressure, utilizing closed-cycle propylene refrigeration. The objective is to obtain a high % recovery of high purity ethylene. This process is a high energy user and costly. C3 Splitter (C3H8 C3H6) This involves the separation of propylene form propane. High pressure, typically 220 psia, is needed to condense the propylene vapor at ambient temperatures around 40C and allows the use of cooling water on the condenser. C4 Splitter (iC4H10 nC4H10) This involves the separation of i-butane form n-butane. Naphtha Splitter Full Range Naphthas (FRN) feed is taken from the crude unit overheads and the splitter separates the light from the heavy naphtha. Light naphtha from the overheads is cooled against the incoming FRN and then condensed in air fin fan coolers and used as reflux or routed to the light naphtha stabilizer column for stabilization and recovery of light ends LPG. The column uses a forced circuit fired reboiler system. The splitter bottoms are pumped via a heat exchanger to recover heat from the Naphtha Hydrotreater hot reactor effluent into a fired furnace to provide the desired reboiler duty to effect the separation of the light and heavy naphthas. Heavy naphtha from the column bottoms is fed to the Naphtha Hydrotreater section and subsequently the Catalytic Reformer feedstock. The thermodynamics suitable for simulating these hydrocarbon mixtures are the equation of states Soave Redlich - Kwong (SRK) for pressures >1 bar and Peng Robinson for pressures >10 bar.

15

Case R5.01 Deethanizer (4) Ethane is the primary component in the feed to olefin plants for the production of unsaturated hydrocarbons such as ethylene. = + Methane and ethane are to be separated from propane using 48 theoretical stages with the feed being introduced on tray15. Integral condenser is stage 1 and reboiler stage 48. Column top pressure is 18.33 bar but tray pressure drop was not included. Feed composition and conditions are shown in Stream 1. Suitable thermodynamics are SRK or Peng Robinson. Reference (4) indicated good agreement with both methods but the prediction, by both methods, of ethane composition in tower bottoms was inaccurate leading to a higher ethane recovery than on plant The column operating conditions are to be established to achieve the following separation. C2 Splitter Operating Targets Overhead Bottoms Component mole fraction mole fraction methane 0.241 0 ethane 0.738 0.0022 propane 0.0106 0,9914 i-butane 0 0.00555 n-butane 0 0.00085 H2S 0.000047 0 The SCDS convergence parameters were set for a distillate propane composition 1.4 reflux ratio and a bottoms ethane composition 0.0022 mass fraction. The column converged with a reboiler duty of 3461 MJ/h. Tray composition profile is shown.

16

Case R5.06 C4 Splitter Tray Column The previous data has been based on an industrial fractionator; reference: Klemola and Ilme, Ind.Eng.Chem.35, 4579 (1996) with tray specification as follows: Key Tray Specifications Downcomer Area (centre) m 51.8 Tray Spacing m 2.9 Hole Diameter no 74 Total Hole Area m 1.859 Outlet Weir Height m 2.885 Tray Thickness m/pass 0.967 2 Number of Valves m 4.9 m2 0.86 Free Fractional Hole Area

Column Height Column Diameter Number of Trays Weir Length (side) Weir Length (centre) Liquid Flowpath Length Active Area Downcomer Area (side)

m2 m mm m2 mm mm no/tray %

0.86 0.6 39 0.922 51 2 772 18.82

SCDS simulation model is now changed to Tray Column Mass Transfer and the tray details are entered as shown. Tray efficiency profiles were not entered but 85 to 90% is typical. The side weir dimension is as shown in the diagram below and is not to be confused with side weir length. Note that the Downcomer side area shown in the table is for 2 passes.
Area 0.43 0.335 1.859 2 Passes

The total hole area is shown as 0.922m2 which is in ratio to the active area of 4.9m2 giving the free fractional hole area of 18.82%. The simulation is now shows the following results:

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Section 6 Hydrotreater
Case/File Name R6.01 Hydrotreater Simulation Description Hydrotreater

References 1. J.A.Moulijn, M.Makkee, A.Van Diepen, Chemical Process Technology, Wiley, 2001. 2. G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000. 3. W.L.Nelson, Petroleum Refinery Engineering, 4th Edition, McGraw Hill, 1958. Process (1, 2) Hydrotreaters are used to selectively remove undesirable elements and hydrogen saturate unsaturated components. Reactor pressures vary 500-1000psig and temperatures 550-700F. Hydroteating involves reaction with hydrogen to remove mainly sulfur, nitrogen and oxygen with some hydrogenation of double bonds and aromatic rings taking place. Hydrotreating is always applied as a pre-treatment to naphtha reforming to protect the catalyst against S-poisoning. Hydrotreating of heavy residues is not considered here. H2 reacts with mercaptans (1H2), thiophenes (3H2) and benzothiphenes (5H2) produce H2S H2 reacts with pyridine (5H2) produces NH3 H2 reacts with phenols (1H2) produces H2O Hydrotreater Hydrogen Usage and Losses (2) Units scf/barrel fresh feed sm3/m3 fresh Remarks Reactions(basis fresh feed 100 500 18 -89 Unsaturated components >H2 Solubility(basis fresh feed) 10 - 20 1.8 3.6 Purge 40 - 100 7.2 - 18 Depend H2 in makeup gas Recycle 500 - 1500 89 - 267 Maintain H2/hydrocarbon ratio The flow sheet is similar for all hydrotreating operations. The liquid feed stock is mixed with a hydrogen-rich gas and preheated by exchange with the reactor effluent. The warm feed is brought to the desired reaction temperature in a furnace and fed to the hydrotreating reactor. The reactor effluent is cooled and the hydrogen-rich gas is separated from the liquid product. The separator liquid is sent to a fractionator for removal of dissolved light hydrocarbon liquids and gases.

18

Case R6.01

Hydrotreater Unit

Simulation flowsheet

Simulation Parameters Thermodynamics selection is K-SRK and L-SRK. Pseudocomponents are created for the feed (FEEDC6+) and product (PRODC6+) streams based on predicted molecular weight, API gravity and normal boiling point.

19

Section 7 Catalytic Reformer

Case/File Name R7.01 Reformer Simulation Description Catalytic Reformer

References 1. G.L.Kaes, Refinery Process Modelling, Athens Printing Company, 1st Edition, March 2000. 2. A.Askari et al, Simulation and Modelling of Catalytic Reforming Process, Petroleum & Coal ISSN 1337-7027. Process Description A traditional reforming process uses three fixed bed reactors in series. Endothermic dehydrogenation reactions take place in the first two reactors requiring fired inter-heaters to raise the temperature for the following reactor with hydrocracking reactions being significant in the final reactor. Reforming catalysts are subject to poisoning by hydrogen sulphide and other sulfur compounds, nitrogen, and oxygen which are removed from the naphtha by mild hydrotreating. The primary reformer feed stock is virgin (uncracked) naphtha from the crude distillation process and other naphtha stocks of suitable boiling point range are acceptable after hydrotreating. The reactions do not occur evenly through the reactors so it is the convention in simulation work to consider all the reaction taking place in the last reactor. Reactors 1 and 2 are set up for mass transfer with the pressure drop being entered and the isothermal mode being used to set the outlet temperature. Using the initial reactor inlet composition for the inter-furnace duty calculations does not result in significant inaccuracies. The final reactor is set up in adiabatic mode with the kinetic reactions specified. Pre-treated naphtha is combined with recycle gas with H2 composition in range 75 to 85 mole % and preheated by exchange with the effluent from reactor 3. Typical reactor pressures and temperature drops are shown: Operating Data Inlet temperature F Inlet pressure psia Measures T (Typical) F Recycle MMSCFD Catalyst Volume ft3 Reactor 1 937 413 60 (90-130) 0.5-1% Naphtha Feed 274 Reactor 2 937 394 35 (40-60) 411 Reactor 3 937 394 25 (1) (10-20) 910

Note 1 Simulation temperature drop is much larger due to the example reactions considered The temperature drops across the reactors are monitored to track catalyst activity. Separator parameters The separator feed is cooled to 90 - 100F using air and water coolers and the flash drum pressure was run at 290 psia and with isentropic flash. The hydrogen rich gas stream is used in other refinery operations and compressed and remainder recycled to the process where it combines with the naphtha feed prior to the feed/effluent heat exchanger. Operating Data Temperature F Pressure psia H2 Purity Separator 100 290 0.79

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Stabilizer parameters The liquid is feed to the stabilizer to remove the light ends. Reformer stabilizers generally have 30 to 36 actual trays with overall tray efficiencies in the range 70 to 75%. The primary function is to strip the n-butane from the reformate product. The distillate is sent to a gas recovery plant and the column bottoms product is stabilized reformate. Operating Data Number of stages Feed tray Feed temperature F Tray 1 temperature F Bottom temperature F Partial condenser pressure psia Stabilizer 36 19 297 257 446 (Simulation 488) 239

To indicate the principles of configuring the catalytic reformer the following stoichiometric equations have been used.

Refer to Section 1 for a more detailed analysis of refinery chemistry. It is recognised that the compositions do not represent typical conditions and is an over simplification of the number of species and the complexity of the kinetic reactions involved. In practices there are many reactant components and intermediate products which make it extremely complicated to study rigorously. To reduce this complication reactants are classified into definite groups as pseudocomponent streams. There are many models available for the study of reaction kinetics including Langmuir-Hinshelwood, Arrhenius and Smith. The Smith model considers the following groupings: Naphthene + H2 Paraffin Naphthenes Aromatics + 3H2 Hydrocracking of paraffin Hydrocracking of naphthenes Pseudocomponent groupings will include specific boiling ranges such as for C6 to C11 paraffins, C6 to C11 naphthenes, benzene, toluene and C8 to C11 aromatics.

21

Case 7.01 Catalytic Reformer Flowsheet is shown:

Thermodynamics selected:

K-Peng Robinson

H-Peng Robinson

The configuration for catalytic Reactor 3 is shown.

22

Section 8 Amine Treatment

Case/File Name R8.01 Vacuum Still Simulations Description Sour Gas Treatment

References 1. A.Kohl and R.Nielsen, Gas Purification, Gulf Publishing , 5th Edition, 1997 Process Chemical absorption of CO2 and H2S with amines provides the most cost effective means of obtaining high purity vapor from sour gases in a single step. The process is well established for refinery gas sweetening which are carried out at high pressures. Several alkanolamines such as MEA (monoethanolamine), DEA (diethanolamine) and MDEA (methylydiethanolamine) have been used, with the selection being determined by the application. The speciality amine aqueous solution strength can vary in the range 15 to 50% and can have a significant effect on the process economics. Generic amines, such as MEA and DEA, are more corrosive and strengths are limited to 30%. The higher the solution strength the liquid circulation requirement is reduced. Steam consumption is highly dependent on this selection, with lower concentrations requiring more steam. The boiling point for regeneration increases at higher MEA concentrations which greatly increases the rate of corrosion of common metals. Also MEA tends to degrade as the temperature rises, increasing the replacement expense and involving the removal of degradation products. MEA has a substantially higher vapor pressure than other amines and a water wash at the top of the absorber can be used to minimize amine losses. The Lean Amine Feed temperature can have a significant influence on the amine losses. A typical gas sweetening flowsheet using amine solution is shown. It consists of an absorber in which cooled lean solvent flows downward contacting with the upward flowing gas to be treated. The rich liquid leaves the absorber at a higher temperature due to the heats of solution and reaction and is preheated with stripper bottoms prior to being fed to the reboiled stripping column. The overhead stripped gas is cooled to remove water vapor which is returned to the column to maintain the water balance. If the gas stream to be treated contains condensable hydrocarbons the lean amine temperature should be above the dew point temperature to prevent condensation of an immiscible hydrocarbon liquid which will promote foaming in the absorber.

23

Section 9 Miscellaneous Application

Case/File Name R9.01 Biodiesel Blending Diesel is blended with Methyl Ester (ME) during ship offloading. The diesel composition in the ester can vary from 0 to 20%v/v and the product blend ester composition is in the range 5% to 15%v/v. The ship discharge flow can vary from 800m3/h to 1000 m3/h at a maximum pressure of 10 barg. The mass balance on the streams give: Miscellaneous Application Simulations Description Biodiesel Blending

DE E DS
Where: DE E VE DS VP Diesel in Methyl Ester Flow (m3/h) Methyl Ester Flow (m3/h) Methyl Ester Volume Fraction Diesel Flow from Ship (m3/h) Bio-diesel Product Volume Fraction

VE

DE + E VP DS + DE + E

We have:

Rearranging gives:

E E and VP = E + DE E + DE + DS E 1 VE and substituting for DE leads to the following: DE = VE DE + E 1 V P DS and = E = (V E V P 1) 1 VP VE DS VE =

Methyl Ester % 100

Ester Blend to Ship Flow Ratios Product Blend VE / VP % 15 10 5 15 10 5 6.667 10.0 20.0 5.33 8.0 16.0

80

Ship to Ester Blend Flow Ratio 0.176 0.111 0.053 0.231 0.143 0.067

A process control system would set the blender flow ratios by entering the ME blend (VE) and Final Product blend (VP). The ME blend flow (E+DE) required for a wild Ship Discharge flow (DS) is calculated. The flow ratio controller would manipulate the ME flow to achieve the desired ratio. In the simulation the blend actual ME component standard liquid volume fraction and the product ME standard liquid volume fraction are set in the appropriate controllers.

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Case R9.01 Biodiesel Blender Simulation The physical property data used are shown. The ship diesel temperature can vary in the range 15C to 40C. Thermodynamics used were K- UNIFAC and L- Latent Heat. Fluid Physical Property Data at 15C Density kg/m3 807.15 876.43 864.74

Fluid Diesel Methyl Ester !00% Methyl Ester 80%

Viscosity cps 2.78 7.48 5.72

The controllers are configured as shown:

The simulation results are in accordance with the theory developed above.

The maximum and minimum ester blend flowrates obtained are 230.7 and 42.1 m3/h.

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Section 10 General Engineering Data

Contents Units Refinery Process Overview Commercial Steel Pipe ANSI B36.10:1970 & BS 1600 Part 2: 1970 Typical Overall Heat Transfer Coefficients Typical Fouling Resistance Coefficients Heuristics for Process Equipment Design Process Simulation Procedures and Convergence References 1. Crane Co., Flow of Fluids Through Valves, Fittings and Pipes, Publication 410, 1988 Units Volume The basic measurement for crude oil liquid volume is referred to as a barrel (bbl). CHEMCAD unit converter feature by selecting Fn f6 allows conversion between units as shown:

Gas Constant R 8.314 J/K-mol API gravity formulae API gravity (API ) of petroleum liquids is determined from specific gravity (SG) at 60F: = 141.5 131.5 1.986 Btu/R-lbmol 0.73 ft3 atm/ R lb mol

The specific gravity of petroleum liquids can be derived from the API gravity: = 141.5 + 131.5

Heavy oil with a specific gravity of 1.0 (density water at 60F) has an API gravity of: 141.5 131.5 = 10 Crude oil is often measured in metric tons (1000kg). The number of barrels per metric ton for a given crude oil based on its API gravity is calculated from: 141.5 = 1 0.159 + 131.5 Where 1 bbl = 0.159 m3 A metric ton of West Texas Intermediate 39.6 API would contain about 7.6 barrels.
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Reid Vapor Pressure (RVP) A measure of gasoline volatility being defined as the absolute vapor pressure exerted by a liquid at 100F(37.8 C) as determined by the test method ASTM-D-323. The test method applies to volatile crude oil and volatile non-viscous petroleum liquids. Cetane Index Based on the density and distillation range ASTM D86 of a hydrocarbon using two methods ASTM D976 and D4737 (ISO 4264). Cetane index in some crude oil assays is often referred to as Cetane calcule, while the cetane number is referred to as Cetane measure. Aniline Point Defined as the minimum temperature at which equal volumes of aniline and oil are miscible to give an estimate of the content of aromatic compounds in the oil. The lower the aniline point, the greater is the content of aromatic compounds. VABP and MeABP Petroleum fractions are cuts with specific boiling point ranges, API gravity and viscosity. Each cut can be divided into narrow boiling fractions called pseudo-components where the average boiling point can be estimated as either mid-boiling point or mid-percentage boiling point. The TBP curve is divided into an arbitrary number of pseudo-components or narrow boiling cuts. Since the boiling range is small both mid-points are close to each other and can be considered as the VABP or MeABP for that pseudo-component. Five different average boiling points can be estimated on the distillation curve. The volume average boiling point (VABP) and the mean average boiling points (MeABP) are the most widely used. VABP is calculated from the ASTM D86 distillation and is the average of the five boiling point temperatures (F) at 10, 30, 50, 70 and 90% distilled:

=
MeABP is calculated from: Where is given by:

+ + + + 5

= 0.94402 0.00865 32. + 2.99791. = 90 10

MeABP (R) is used in the definition of the Watson K which is given by:

=
Factors Note 1 10-12 10-9 10-6 10-3 10-2 10-1 101 102 103 106 109 1012 E-12 E-09 E-06 E-03 E-02 E-01 E01 E02 E03 E06 E09 E12

/
Prefix pico nano micro milli centi deci deca hecto kilo mega giga tera Symbol p n m c d da h k M Note 2 G T

Note 1 Tip for setting power, make equal to number 0s so 0.00001 = 10-5 and 100000 = 105 Note 2 Refinery industry practice sometimes uses MM to signify 106

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Heuristics for Process Equipment Design In modelling, Rules of Thumb or heuristics based on experience, are used for estimating many parameters before more specific data is available. Piping Design Industry practice for initial design of piping systems is based on economic velocity or allowable pressure drop P/100ft. Once detailed isometrics are available the design will be adjusted to satisfy local site conditions. Reasonable Velocities for Flow of Fluids through Pipes (Reference Crane 410M) Reasonable Velocities Pressure Drop Service Conditions Fluid m/s ft/s kPa / m Boiler Feed Water 2.4 to 4.6 8 to 15 Pump Suction & Drain Water 1.2 to 2.1 4 to 7 Liquids pumped General Service 1.0 to 3.0 3.2 to 10 0.05 Non viscous Saturated Steam Heating Short Lines 20 to 30 65 to 100 0 to 1.7 bar Saturated Steam Process piping 30 to 60 100 to 200 >1.7 bar Superheated Steam Boiler and turbine leads 30 to 100 100 to 325 14 and up Process piping Gases and Vapours 15 to 30 50 to 100 0.02%line pressure Process piping Liquids gravity flow 0.05 Reasonable velocities based on pipe diameter Process Plant Design, Backhurst Harker p235 Pump suction line for Pump discharge line for Steam or gas d in d in d in (d/6 + 1.3) ft/s (d/3 + 5) ft/s 20d ft/s d mm d mm d mm (d/500 + 0.4) m/s (d/250 + 1.5) m/s 0.24d m/s

Heuristics for process design Reference W.D.Seader, J.D.Seider and D.R.Lewin, Process Design Principles are also given: Liquid Pump suction Liquid Pump discharge Steam or gas (1.3 + d/6) ft/s (5.0 + d/3) ft/s (20d) ft/s 0.4 psi /100 ft 2.0 psi /100 ft 0.5 psi /100 ft

Air for combustion, unless otherwise stated, is at ISO conditions of 15C, 1.013 bar and 60% relative humidity. Air for compression is defined at Free Air Delivery(FAD) conditions of 20C, 1 bar and dry. Pumps Centrifugal pumps: single stage for 15-5000 gpm, 500 ft max head. Centrifugal pumps: multistage for 20 11,000 gpm, 5500 ft max head. Efficiency 45% at 100 gpm, 70% at 100 gpm and 80% at 10,000 gpm.

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Process Simulation Procedures and Convergence Steady state simulation proves the capability to achieve stable and reproducible operating conditions with acceptable product purity, yield and cycle times to satisfy the commercial requirements and the safety and environmental issues for the regulatory authorities. A process simulation involves taking the input stream flow rates, compositions and thermodynamic conditions, performing a series of iterative calculations as the streams are processed through Unit Operations and recycles, finally leading to the output stream flow rates, compositions and thermodynamic conditions. Feeds Recycles Products

The chart below shows the basic steps involved in setting up a steady simulation.

It is recommended that the SCDS UnitOp is used for building fully integrated models because it has a greater number of connection points. SCDS 1 and SCDS 21-24 icons are the most developed having built in dynamic vessels and control loops. However for our initial exercise we will use SCDS Column 1 icon. For refinery operations the Tower UnitOp is more suitable as it includes pump around and stripping facilities. The stage numbering convention in CHEMCAD is from top to bottom, 1 to N. A stage is considered the space above a plate. If a condenser is present it is stage 1; if a reboiler is present it is stage N. To model a column which has ten stages plus condenser and reboiler 12 stages (10+condenser+reboiler = 12) must be specified. If a condenser is present, the feed must not enter stage 1, as that is the reboiler. Top stage feeds should enter stage 2, the top stage (plate), if a condenser is present. Likewise, if a reboiler is present a bottom plate feed is connected to stage (N-1), not stage N. Typically the user has a product specification, mass fraction of a key component in either the bottoms or tops, for a column design or to achieve with an existing column. Converging a column model in simulation is similar to converging a column in the real world; it is difficult to go directly to high purity separation. It is best to start with an easy target, such as reflux ratio and bottoms flowrate. Once the column is converged to this simple specification, we tighten the specifications toward the target specification. Use the following procedure:
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1. 2. 3. 4. 5.

6.

Set up the column: number of stages, condenser, reboiler, operating pressure. Generate TPxy and RCM plots to verify that the target is thermodynamically feasible with the selected VLE K model. On the SPECIFICATIONS page, set loose specifications such as Reflux Ratio and Bottoms Flowrate or Reboiler Heat Input. Run the column and converge. Change the specifications if necessary. Go to the CONVERGENCE page of the column dialog. Set the initial flag to 0 Reload Column Profile. This setting instructs CHEMCAD to use the current converged profile as its starting point (initial conditions) in iterative calculations. On the SPECIFICATIONS page change to more tight specifications. Run the column.

If the column converges, tighten the specifications and run again. If the column fails to converge, do not save the profile of the failed attempt. Relax the specifications and run the column again. Repeat from step 5 until you reach the target. Often, it is difficult to obtain the first convergence on a column. If the column is run with no condenser or reboiler, one does not have the option of loose specifications. If the column has a condenser or reboiler, relaxing specifications does not always help. 1. On the convergence page of the column dialog, specify estimates if you can make reasonable estimates. Note that a bad guess will make the column more difficult to converge than no estimate. Remove non key components from the feed(s) to obtain the first convergence. Now set the initial flag to 0 Reload Column Profile, return the other components, and run the unit again. Specify a larger number of iterations on the convergence page of the column dialog. The default is 50, but possibly 52 iterations will find the answer. Try an alternate column model. If you are currently using the SCDS try the same separation with a TOWER or vice versa. The two models use different mathematical models; often one will find an answer in 10 iterations while the other is difficult to converge. It is not possible to obtain different answers with the columns; the models are numerical methods to find a stable composition profile. Consider a partial condenser. If you have a condenser present but have a significant amount of light ends, you may have difficulty converging the column. The default condenser type, total, requires that no vapor leaves stage 1. If light ends are present, this may not be possible without cryogenic temperatures. Changing condenser mode to partial allows the light ends gases to slip past the condenser.

2. 3. 4.

5.

30