Oilfield Water Handling, Treatment and Re-Injection

Mukul M. Sharma
Professor Department of Petroleum & Chemical Engineering

University of Texas at Austin

Produced Water
Produced water is a byproduct of oil and gas production. Each barrel of oil produced generates 7-10 barrels of water1. Composition depends on geographical location, but primary components of produced water often include:
Dispersed oils Soluble organics such as organic acids, aromatic hydrocarbons, phenols, and/or volatiles Salt Treatment chemicals such as emulsion breakers, corrosion inhibitors and biocides Produced solids such as clay, sand, silt, and carbonates Metals

1. Veil, J. A.; Puder, M. G.; Elcock, D.; Redweik, R. J.; U.S. DOE, 2004; pp 3-10.

Size and Nature of the Problem

Produced water is the largest single wastewater stream in oil and gas production More than 14 billion barrels processed in U.S. alone in 2002 Produced water is often polluted due to contamination with salts, emulsified oils, etc.
Unfit for human consumption Unfit for agricultural use Cannot be directly discharged

Subsurface injection is often the most viable disposal option

Injection costs vary from $0.75 - $1.50 per barrel
Produced water discharges to the North Sea: Fate and Effects in the water column, Summary Report, http://www.olf.no/static/en/rapporter/producedwater/2.html Rawn-Schatzinger, et al., GasTIPS, 9, pp. 13-18 (2003). Rawn-Schatzinger, et al., GasTIPS, 10, pp. 9-14 (2004).

Oilfield Water Handling, Treatment and Re-Injection

Two major efforts at UT: Water Re-Injection Research
Industry funded

Fouling-Resistant Membranes for Produced Water Purification

DOE and industry funded

Water Re-Injection Research Program

Injection Well Models Core flow tests

Combining single well models with reservoir simulators

Large block tests

Distributed Models

Oily Water Injection

Horizontal /Multilateral Injectors

Injection Into Soft Sands

Case Studies

Fouling-Resistant Membranes for Produced Water Purification

Benny Freeman, Mukul Sharma, Elizabeth Van Wagner, Alyson Sagle

The University of Texas at Austin

Opportunity
Produced water often generated in arid regions (e.g., western U.S.) where water could be used for
Human consumption Wildlife and livestock watering Crop watering Recreational use

Estimated cost to treat produced water by RO is $0.08-$0.10 per barrel If treatment cost of produced water decreased, useful economic life of oil and gas fields increase Potential show-stopping issue: RO membrane fouling by produced water
Produced water discharges to the North Sea: Fate and Effects in the water column, Summary Report, http://www.olf.no/static/en/rapporter/producedwater/2.html Rawn-Schatzinger, et al., GasTIPS, 9, pp. 13-18 (2003). Rawn-Schatzinger, et al., GasTIPS, 10, pp. 9-14 (2004).

Produced Water: Problem or Opportunity

Undesirable Management of Produced Water Beneficial Use of Produced Water

Eye on Environment, 7(2), Summer 2002, US DOE, NETL.

Purification of Produced Water: Approach

Begin with commercial RO membranes, which have excellent rejection for salts, oil, etc. Modify surface of membranes to resist fouling
Graft fouling-resistant brushes to surface Coat with fouling-resistant polymers

Project Tasks
Characterize oil-water emulsions Select RO membranes for modification Develop/refine grafting and coating chemistry Prepare and test coated or surface modified membranes

Emulsion Characterization
Determine size and size distribution of emulsions
Problem: no single analytical technique is good for entire distribution
Dynamic light scattering: <1 m diameter Coulter counter: >0.8 m and <4 m Optical microscope: >~1 m

Approach: use all three techniques to characterize emulsion

Determine effect of oil/surfactant ratio, concentration, and blending time on size distribution, and stability Standard conditions
1500 mg/L soybean oil, DC 193 non-ionic surfactant mixture 9:1 oil:surfactant ratio Mix for 180 s in high speed blender

Optical Microscopy

1,500 ppm

15,000 ppm

Size Characterization
Number Average Diameter,
N d = N
4 3

Dn

N d Weight (or Volume)Average Diameter, D = N d

v

Polydispersity (PD),

Dv PD = Dn

Example Optical Microscopy Results

Blending time was fixed at 180 seconds

Coulter counter results for standard recipe

Dn (m) 1. 2. 3. 1.15 1.15 1.16

Dv (m) 1.54 1.54 1.55

Number distribution and volume distribution for the emulsions prepared by standard recipe (1500 ppm, 9:1, 180s). 3 duplicate runs were performed and shown on the graphs.

Coulter Counter Measure of the Effect of Concentration and oil/surfactant ratio on Size and Distribution

Blending time was fixed at 180 seconds

Correlation Between Optical Microscopy and Coulter Counter Results

Sample Dynamic Light Scattering Results

Correlation Between Coulter Counter and Dynamic Light Scattering Results

Emulsion Characterization Results

Emulsion concentration, oil/surfactant ratio and blending time influence emulsion properties Oil emulsions with smaller particles and narrower particle size distribution can be achieved by decreasing emulsion concentration, increasing surfactant and increasing blending time Baseline emulsion formulation (1350 ppm soybean oil, 150 ppm DC-193, blended for 180 s) stable for at least 2 weeks.

Membrane Modification: Approach1: Grafting

Literature Data: PEG diepoxide-treated RO Membranes

H2C
HC
H2C

OCH2CH2

OCH2
n

CH

CH2

PEG diepoxide Concentration (%) (n75, mw3400) 0.0 (not heated) 0.0 (60oC) 1.0 (60oC) 2.0 (60oC) 4.0 (60oC)

NaCl Rejection (%) 99.0 99.3 99.7 99.4 99.6

Permeance (L/(m2h bar)) 3.23 2.46 0.664 0.524 0.514

Mickols, William E. U.S. Patent 6,280,853 B1 2001. Test conditions: 2000 ppm NaCl feed, p = 225 psi.

GE Infrastructure Water & Process Technologies Commercial RO Membranes

Formerly GE Osmonics GE Series A Brackish Water Reverse Osmosis Membranes Polyamide thin film composites on polysulfone support
Typical Feed Pressure (psig) Typical operating flux (L/m2hr) Average NaCl Rejection (%)
O C O C N H H N

200 15-35 99.5

O C O C N H N

SEM image of AG membrane

y
H

C OH

(www.desalwater.com)

Composition of AG RO Membrane
XPS Data (mol%) C N O 74.61.2 10.40.2 14.61.0
and x+y =1
N H O C O C N H H N O C O C N H N

y
H

C OH

C NH

Example: N 2 x + 3 y 10.4 = = O 4 x + 3 y 14.6

Solve for x and y: x = 0.560.25 y = 0.44 0.25

% Carboxylic acid groups (CA) = 18.7% 8.3 Koo et al. report 9.3%1.2 CA for a similar membrane (FT-30).

Koo, J.; Petersen, R. J.; Cadotte, J. E. Polymer Preprints 1986, 27, 391.

Tethering Brushes to RO Membranes React Epoxides with Terminal Amines

O HN NH C O C NH NH O C O C NH NH2

OH

1-n
H2C O HC R

O HN NH C

O C NH NH

O C

O C NH NH CH2

OH CH R

OH

1-n

PEG Diepoxide Treatment

Soak membrane in deionized water for ~24 hrs, changing water occasionally, to remove glycerin. Heat water to 40oC. Add poly(ethylene glycol) diglycidyl ether (PEG diepoxide) to water; let stir for 5 minutes. Submerge membrane in solution for 10 minutes while maintaining temperature (no stirring). Remove membrane; rinse ten times with deionized water, shaking to remove unreacted PEG diepoxide; store membrane in deionized water.

Effect of Diepoxide Grafting Solution Concentration on Contact Angle of GE AG RO Membrane

70 60 Contact Angle ( o)

Contact angle: decane drop in water. Contact angle decreased strongly at low diepoxide concentration

50

40

30

20

10

20

30

40

50

PEG diepoxide Concentration (vol%)

H2C

HC

H2C

OCH2CH2

OCH2
n

CH

CH2

PEG diepoxide (n 9, mw 526)

Crossflow Data: Untreated vs. PEG diepoxide-treated FilmTec Membranes

8 Average permeance (L/(m h bar)) 7 6 5 4 3 2 -0.5 n=600 0.12 wt% top surface (XLE) n=600 0.04 wt% (XLE)
Normalized average permeance 1 n=600 0.12 wt% (XLE) 0.95

XLE control

0.9 n=600 0.04 wt% (XLE) n=600 0.12 wt% top surface (XLE)

0.85

0.8 XLE control 0.75 -0.5 0 0.5 1 1.5 2 2.5

n=600 0.12 wt% (XLE) 0 0.5 1 1.5 2 2.5

Permeation time (hrs)

Permeation time (hrs)

Initial conditions: pure water plus 2000 ppm NaCl. At t = 0, added 25 ppm dodecane/25 ppm SLS emulsion. 25oC, 0.6 gpm, pH 7.7, p = 150 psi.

12

NaCl Rejection: Untreated vs. PEG diepoxide-treated FilmTec Membranes

100 n=600 0.12 wt% (XLE) Average NaCl rejection (%) 99.5 n=600 0.04 wt% (XLE)

99

98.5

n=600 0.12 wt% top surface (XLE) XLE control

98

0.5

1.5

2.5

Permeation time (hours)

Initial conditions: pure water plus 2000 ppm NaCl. At t = 0, added 25 ppm dodecane/25 ppm SLS emulsion. 25oC, 0.6 gpm, pH 7.7, p = 150 psi.

PEG diepoxide-treated AG RO Membranes

PEG diepoxide Concentration (vol%) 0 0 2 4

Treatment Temperature (oC) room temp. 40 40 40

Contact Angle (o) 67 3 59 6 42 3 39 1

Flux (L/(m2 h)) 12.5 10.2 2.8 2.3

Permeance (L/(m2 h bar)) 3.6 3.0 0.81 0.66

Dead End Experiments with PEG diepoxide-treated GE AG RO Membranes

Comparison of pure water and 150 ppm surfactant (DC193) solution fluxes for untreated (0 vol% room temp.) vs. treated (2 vol% PEG diepoxide, 40oC) membranes.
Flux of untreated membrane decreases by 2.5x for surfactant solution vs. pure water. Flux of PEG diepoxide-treated membrane decreases by <20%.
20

15 Flux (L/(m 2h))

0 vol% room temp. pure water

10
0 vol% room temp. 150 ppm surfactant

2 vol% 40 C pure water 2 vol% 40 C 150 ppm surfactant

o

2 4 6 8 Permeation Time (hours)

10

p=50 psi

Preliminary Crossflow Results

25 20 Permeate Flux (L/m hr)
2

Increase Pressure to 225 psig

100 Add more organic Organic Rejection (%)

Graft

Control

99.8 Coated 99.6

15

Control Coating

10 Graft Decrease Flow to 0.5 gpm 40 60 80 100 120 Permeation Time (hr) 140

99.4

99.2

99 20

40

60

80

100

120

140

160

Permeation Time (hr)

Original Conditions: p=150 psi, 1,500 ppm oil/water emulsion, 1.0 gpm

Future Work
Graft PEG with one epoxy endgroup
Synthesize from PEG methacrylate (PEGMA) or PEG methyl ether methacrylate (PEGMEMA), using mchloroperoxybenzoic acid in nonpolar solvent
H3C CH2 C O C OCH2CH2 OH

poly(ethylene glycol) methacrylate (PEGMA)

CH2 H3C C O C OCH2CH2 OCH3

Graft PEG diepoxides of varying chain length Explore pH effects

poly(ethylene glycol) methyl ether methacrylate (PEGMEMA)

O Cl C O OH

Explore isocyanate linking chemistry

m-chloroperoxybenzoic acid

Preparation of Molecules for Grafting

Epoxides1:
Cl O C O OH R CH CH2 R C H O CH2

Isocyanates:
R OH O C N R' N C O R

O O C

H N R' N C O

O R O C

H N R' N C O
+

H O C

H N

H2N

N R' N

1. Reaction conditions: 25oC, dichloromethane (solvent). Koerner, T. et al., Journal of Organic Chemistry, 1999, 64, 196-201.

Summary
Grafting provides a straightforward, practical method to alter surface properties of RO membranes Grafting directly to RO membrane surface yields a material that does not exhibit significant fouling by oil/water emulsions Future studies will focus on developing systematic structure/property relations to prepare optimum coating and grafting strategies to protect RO and NF membranes from fouling by produced water.

Approach 2
Applying coatings
Attach a hydrophilic polymeric film to the surface of commercial RO membrane

Grafting molecules
Graft molecules to commercial RO membrane surface
Hydrophilic molecules Molecules with C=C bonds (i.e. methacryloyl chloride) for future polymerization with hydrophilic molecules or films

UV-Crosslinked Polymeric Coatings

O H2C C H C OCH2CH2 O O C 13 C H CH2
C C C PEO OX O C OX PEO O C C C PEO O C C C O C C O C C C PEO O C C O

Crosslinker: Poly(ethylene glycol) diacrylate

O H2C C H
O H2C C H C OCH2CH2 OCH3 8

C O O

OCH2CH2 7

OH
O

PEO C C

Poly(ethylene glycol) acrylate

Crosslinked PEO

Poly(ethylene glycol) methyl ether acrylate

OH

O H2C C H C OH

O C

Acrylic Acid

UV Initiator: 1-Hydroxycyclohexyl phenyl ketone

Contact Angles in PEG Coatings

Crosslinked PEGDA n=13 60 350 300 Contact Angle in Water ( ) 55 250 50 200 150 100 40 50 35 0 20 40 60 80 wt% Water in Prepolymer Mixture 0 100
0

50/50 PEGDA/PEGA Copolymer 65 60 Water Contact Angle( )

0

400 350 Percent Water Uptake (wt%) 300 250

Percent Water Uptake (%wt)

55 50

45

200 45 40 35 0 20 40 60 80 wt% Water in Prepolymer Mixture 150 100 50 100

As water uptake increases, surface hydrophilicity increases.

Properties of Hydrogels
Contact angle data show hydrophilic nature of PEGDA films
Water Contact Angle ( ) Crosslinked PEGDA 60 350 300 55 Water Uptake (wt%) 250 50 200 150 100 40 50 35 0 20 40 60 80 wt% Water in Prepolymer Mixture 0 100
0

Strong relationship between contact angle and water uptake Previous work has shown increased water transport with an increase in water uptake Copolymers of PEGDA/PEGA and PEGDA/PEGMEA show similar behavior

45

Initial coating work will focus on 100% PEGDA coatings

% water uptake =

mass wet mass dry x100% mass dry

Coating: Problems Encountered

Difficult to produce uniform coatings Most successful coating was approximately 40 microns thick
Desire a coating less than 10 microns to reduce flow resistance
SEM of coated membrane. Measured coating thickness approx. 40 microns.

PEG coatings easy to separate from the membrane

- Need a way to chemically attach PEG coating to the membrane surface

Methacryloyl Chloride Grafting

Treat RO membrane with solution of methacryloyl chloride in solvent of 5% 1,2dimethoxyethane (monoglyme) / 95% decane Allow membranes to soak for various times at room temperature Rinse membranes with de-ionized water to remove residual methacryloyl chloride Take FTIR spectra to determine whether grafting has occurred Surface polymerize a hydrophilic monomer onto treated membranes

Future Work
Refine GMA reaction
Examine shorter reaction times for a more efficient process

Apply PEG coatings to GMA-modified membranes Test modified membranes using oil/water emulsions under crossflow conditions

Oilfield Water Handling, Treatment and Re-Injection

Two major efforts at UT: Water Re-Injection Research
Industry funded

Fouling-Resistant Membranes for Produced Water Purification

DOE and industry funded

Oilfield Water Handling, Treatment and Re-Injection

Questions Comments

Contact Angle vs. Water Uptake in Several Families of Materials

65 50/50 PEGDA/PEGA 60 Water Contact Angle ( )
0

55 50 45 40 35 0 50

PEGDA n=13

PEGDA n=10

100 150 200 250 300 350 400 Water Uptake (wt%)

All chemistries show a similar trend

Coating Apparatus
Drawdown rod PVDF support membrane

Coating speed

Coating Procedure
Variables: rod size (coating thickness) and coating speed. Select the ideal rod size (6m-100m); Mount the support membrane samples on the glass surface and lower the weight arm assembly; Spread the prepolymerization mixture near the rod and coat the support.

Characterization of Coated RO Membrane

Substrate: AG membrane
Water Flux at 50 psig (L/m hr) 8 7 6 5 4 Coated Sample 3 2 0 50 100 150 200 250 300 350 400 Permeation Time (min) Uncoated Sample

Applied PEGDA in 60 wt% water with 2 wt% high MW PEO PEGDA solution thickness ~ 50 microns

Coated Uncoated

Water Contact Angle 52.7 2.1 67.01.0

Angle measured using decane

Pre-filtered water, 50 psig (Lp = 2.2 L/m2 hr bar)

Literature Data: PEG diepoxide-treated RO Membranes

Sample % Flux with Surfactant A 78 89 % Flux after 2 hr Rinse 85 94 % Flux with % Flux after Surfactant 2 hr rinse B with test solution 69 80 84 100

Untreated Treated (0.3% PEG diepoxide (mw200), 50oC)

Test solution (1500 ppm NaCl, p = 150 psi) used for baseline flux; all percentages are compared to this flux Surfactant solutions contain 1500 ppm NaCl and
Surfactant A: 100 mM dodecyltrimethyl ammonium bromide Surfactant B: 100 ppm sodium dodecyl sulfate

First rinse is purified water; flux is of 2000 ppm NaCl solution Flux measured after 3 hrs of treatment, unless stated otherwise

Mickols, William E. U.S. Patent 6,280,853 B1 2001. Test condition: p = 150 psi.

Surfactants
Dodecyltrimethyl ammonium bromide
BrCH3 N+ CH3 H3C

Sodium dodecyl sulfate

O O S OH O

Dead End Experiments with PEG diepoxide-treated GE AG RO Membranes

Stirred cell, 50 psi. Pure water flux. PEG diepoxide-treated membranes (2 and 4 vol% at 40oC) have 4-5 times lower flux than untreated membrane (0 vol% at room temp.).
Flux (L/(m h))
2

14 12 10 0 vol% 40 C 8 6 4 2 0 2 vol% 40 oC 4 vol% 40 oC 0 2 4 6 8 10

o

0 vol% room temp.

Permeation Time (hours)

FTIR-ATR of PEG diepoxide-treated RO Membrane

Spectrum: 0% PEG diepoxide solution spectrum minus 4% PEG diepoxide solution spectrum (both at 40oC) Increases at 2950 cm-1and 1100 cm-1 indicate an increase in alkane and aliphatic ether content, respectively, due to presence of PEG diepoxide on the membrane surface. Decreases in the range from 1400-1800 cm-1 indicate decrease in either free amines or carboxylic acid groups (both groups absorb in this region).

0.015 0.01 Absorbance 0.005 0 -0.005 -0.01 -0.015 3500 3000 2500 2000 1500 1000 Wavenumber (cm )
-1

500

Chemical Attachment of PEG Coatings to RO Surfaces

Using coating machine to control film thickness, spread pre-polymerization mixture on membrane surface, then UV polymerize to form hydrophilic surface layer
Possible membranes:
Original commercial RO membrane Membrane with grafted methacryloyl chloride molecules CH3 O
CH2 C C Cl

Methacryloyl chloride

Methacryloyl Chloride Reaction with Terminal Amines of RO Membranes

O HN NH C O C NH NH O C O C NH NH2

OH

1-n
CH3 H2C C O C Cl

O HN NH C

O C NH NH

O C

O C NH NH

O C

CH3 C CH2

OH

1-n

HCl

Grafting Methacryloyl Chloride

FTIR subtraction spectrum of membrane in solvent from membrane soaked in 25 wt% solution of methacryloyl chloride for 20 hours. Decreases at 1650 and 1100 cm-1 indicate reaction occurs, probably with free amines.
0.01 0.005 0 Absorbance -0.005 -0.01 -0.015 -0.02 -0.025 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm )
-1

Contact Angle Experiments

Ram-Hart NRL Contact Angle Goniometer ( Model 100)

Pendant drop measurements Environmental chamber permits testing in water at controlled temperature Measure equilibrium contact angle

Oil/Water Fouling: Decane Emulsion

12 10 Water Flux (L/m hr)
2

Pure Water

Sample 1 Feed (ppm) Retentate (ppm) Final Permeate (ppm) Final Rejection 1020 1322 6.5 99.5%

Sample 2 1020 2110 11.8 99.4%

8 6 Decane 1 4 2 Decane 2 0 0 100 200 300 400 500 600 Permeation Time (min)

1500 ppm by weight emulsion prepared with 9 parts decane to 1 part Dow Corning Fluid 193 surfactant

AG RO membrane (Lp = 2.8 0.2 L/m2 hr bar) dead-end filtration p = 50 psig

New Linking Chemistries to Access Libraries of Grafting Chemistries

O O Cl C O OH Cl C O O H

O Cl C OH

Reaction Conditions: 25oC, dichloromethane (solvent). Koerner, T. et al., Journal of Organic Chemistry, 1999, 64, 196-201.

Coulter Counter Measure of Emulsion Stability

1500ppm, 6:1, 180s

Contact Angle Measurements: Pendant Drop

Sample Holder Syringe Needle

Reported Angle

Sample

Liquid 2 (Decane)

Liquid 1 (Water)

Background on Contact Angles

Convention is to measure angle through the aqueous phase Water Angle = 1800 Oil Angle
Oil

Water Angle <900 Oil droplet has minimum contact with surface, i.e. surface is hydrophilic

Water

Water Angle >900 Oil droplet has maximum contact with surface, i.e. surface is hydrophobic

Effect of Concentration and Oil/Surfactant Ratio on Polydispersity

Blending time was fixed at 180 seconds

Coulter Counter Measure of the Effect of Concentration on Size and Distribution

Blending time was fixed at 180 seconds

Effect of Concentration and Oil/Surfactant Ratio on Size

Blending time was fixed at 180 seconds