Baker College for Oil Field Application

Water Injection
Water treatments equipments and processes
by Djaffar SI-HASSEN
Content

ƒ Objectives
ƒ Bulk separation
ƒ Produced water treatment
ƒ Seawater and aquifer water
ƒ Injection systems
ƒ Treatments and monitoring
Operational Goals for Water Flood

ƒ Get the water where the oil is

ƒ Maximize injection rates to maintain reservoir pressure

ƒ Lowest possible cost of operation

ƒ Minimize system downtime

ƒ Maintain / improve system integrity

Injection system requirements

Source Water Characteristics Reservoir Requirements

Well Water / Rock

Water Scale
Workovers Interactions
Analysis Control

Injection Reservoir
Microbiological Souring
System
Control
Requirements
Well Inflow Injection
Simulations Test
Solids & Oil Corrosion
Content Control
Filtration
Fracturing
Requirements
Process
Design
Water treatment plant objectives

1. WATER QUALITY AT BOTTOM

2. WATER QUANTITY OF ALL INJECTION
3. WATER PRESSURE WELLS
4. SAFETY
5. ENVIRONMENT
6. RELIABILITY - MAXIMISE AVAILABILITY
- MINIMISE
REPAIR/REPLACEMENT
(FROM CORROSION)
7. COST-EFFECTIVE - OPTIMUM CAPEX/OPEX
Water Flood Potential Problems

ƒ INJECTIVITY
Loss of injectivity due to (suspended solids, mineral
scales, organics, biofouling)

ƒ INTEGRITY
Loss of integrity due to corrosion or mechanical
failure

ƒ SOURING
Reservoir souring due to poor injection water
quality
 Injectivity

ƒ Pore volume (PV) method provides good

estimate for ultimate water requirements

ƒ Volume of water should range from 150 to

170% of total pore space

ƒ Rule-of-thumb is remove particles larger than

1/3 the average pore throat diameter
Average pore throat diameter in microns estimated by square
root of formation permeability in md.
Water Flood Process
Bulk separation

ƒ Gravitational separation
ƒ Centrifugal separation
ƒ Downhole / Subsea separation
ƒ Further treatment
Produced water treatment

ƒ Filtration
ƒ Flotation
ƒ Corrugated Plate Interceptor (CPI)
ƒ Hydrocyclones
ƒ Coalescers
ƒ Centrifuge
ƒ Degassing
ƒ Chemical treatment
Produced water treatment

ƒ Solids Removal
– Suspended Solids
– Scale Control
ƒ Gas Removal
ƒ Bacteria Control
ƒ Corrosion Control
Produced water treatment

Solids Removal
Guideline for solids removal

ƒ Rule –of- thumb is remove particulates larger than 1/3

the average pore throat diameter
9 Average pore throat diameter in microns estimated
by square root of formation permeability in md

Example:
If the formation permeability is 100 millidarcies, then the average
pore throat diameter is estimated at 10 microns. Thus, the
injection water should have no particulate matter greater than
3.3 microns.
Filtration
Filtration
Chemical effects on filter performance

CHEMICAL PARTICULATE REMOVAL

EFFICIENCY
(in aerated seawater)

>1µ >2µ

NONE 60 70

CHLORINE 85 93

+POLYELECTROLYTE 93 98

+COAGULANT 97 99
Filter aids dose rates (in aerated seawater)

ALL CHEMICALS HAVE OPTIMUM RATES FOR

MAXIMUM FILTER EFFICIENCY

Typical rates:
ƒ Chlorine residual 0.3 - 0.6 ppm
ƒ Coagulant 0.1 - 0.5 ppm as Fe3+
ƒ Polyelectrolyte 0.1 - 0.5 ppm as 100% chemical

TOO HIGH OR TOO LOW DOSES

GIVE LOWER EFFICIENCY
Filter aid: optimising of dose rates

ƒ Initially set during commissioning, but may vary

with:
– pH
– Suspended solids concentration
– ‘Plankton blooms’
– Different chemical products
Seawater and aquifer water

ƒ Biological control
ƒ Sulphate control
ƒ De-O2
Biological Control
Biological Activities

ƒ Fish
ƒ Seaweed
ƒ Marine crustacea
ƒ Barnacles
ƒ Plankton

ƒ Sulfate Reducing bacteria

ƒ General aerobic & aneorobic bacteria
ƒ Sulfur oxidising bacteria
ƒ Acidic producing bacteria
First Defence – Antifouling
Chlorine for aerator water

ƒ Hypochlorite
‰Chlorination unit
‰Inject Hypochlorite
‰Inject Chlorine Gas
ƒ Disadvantages
‰ Not good in presence of biofilm
Biofilm Formation Mechanism

Glycocalyx formation
Surface conditioning

Adhesion of ‘Pioneer’ Bacteria

Mature biofilm, is occupied by

glycocalyx matrix (75-95%)
and bacterial cells (5-25%)
Biofilm Formation

S.W.Borenstein Nace 1984

Problems by SRB

ƒ Increase corrosion pitting

under biofilms

ƒ Potential injectivity losses due

to biofilm blocking pores in
formation rock

ƒ Souring of the reservoir due to

bacterial generated H2S
Biofilm - Flush Velocity

Flush Velocity depend on the double layer or sublayer

Flush Velocity ~ 3-4 ft /sec
Bacteria Control - Biocide

ƒ Acrolein
ƒ Gluteraldehyde ƒ Exclusive to Baker Petrolite
ƒ THPS ƒ Not a biocide – a biostat
ƒ QAC ƒ Active against SRB - metabolic inhibitor
ƒ Isothiazolone ƒ Used in conjunction with conventional biocide
ƒ Nitrate ƒ Family of products - liquid and solid (pellets)

Biocide

Biocide + EnviroSweet

0 20 40 60 80 100 120 140 160 180 200

Gallons per Week
Rationale for sulphate removal for WI

Sulphate control
Rationale for sulphate removal for WI (1)

ƒPrimarily to prevent production well/facilities blockages

by sulphate scale, so saves on:

‰Well workovers

‰Scale inhibitor material costs

‰Scale inhibitor application costs (squeezing)?

‰Pollution from scale inhibitor residues, especially squeeze returns,

and upsets in produced water quality

‰Lost/deferred oil production, due to formation damage, well blockages

and downtime for treatments

‰Also reduces carbonate scales, as reduces Ca2+ and HCO3- in injection

water
Rationale for sulphate removal for WI (2)

‰Reduces injection flowline / well corrosion potential (SRB / MIC)

‰Reduces reservoir souring potential

‰Reduces / prevents sulphide stress corrosion (SSC) in production wells,

flowlines and facilities

‰If no souring, then no FeS to stabilise emulsions, so improved produced

oil and water qualities

‰Reduces / prevents need for sweetening chemicals and processes, for

gas, oil and water phases
Sulphate removal process options

ƒMSF (multi-stage flash) distillation

ƒRO (reverse osmosis)
ƒEDR (electrodialysis reversal)
ƒNF (nanofiltration)
ƒIon exchange
ƒPrecipitation

9Nanofiltration, i.e. to 0.001 micrometres or 1 nanometre, will remove

‘large’ ions e.g. multi-valent, multi-element SO42-, but allow smaller
ions e.g. Cl- to pass through
9So the water is still saline/brine, but reduced in sulphate (not zero)
9This is the only cost-effective process
Nanofiltration principle

Osmotic
Applied
Pressure
Pressure

Pure Salt Pure Salt Salt

Pure
Water Solution Water Solution Solution
Water
Pure Water
Pure Water

Semipermeable Semipermeable Semipermeable

Membrane Membrane Membrane
(Sulphate Selective) (Sulphate Selective) (Sulphate Selective)
Nanofilter membrane assembly
Nanofiltration module
Sulphate removal process

Regulating
Valve
Seawater
2,800 ppm SO42-
Concentrate or Reject
100 m3/h
Membrane 9,240 ppm SO42-
11,000
30 m3/h

Pressure Vessel
Permeate or Product

40 ppm SO42-
Reproduced with permission of Dow Chemical
70 m3/h
Sulphate removal process

1st Array High

Sulfate Concentrate
50 gpm to 2nd Array Feed
Feed
100% 50 gpm
25 gpm 25 gpm Reject
100 gpm
25 gpm
50 gpm 25 gpm 75 gpm Product
50 gpm

1st Array 2nd Array

50% Conversion 50% Conversion
Girassol sulphate removal facility (1 train)

50K BWPD (8000 cubic meter per day) or 1460 gpm

48.6 gpm
2,860 mg/l SO4
26.1 gpm 27.2 gpm
Feed, 6000 mg/l SO4 11,000 mg/l SO4
1944
gpm

405 gpm
20 Vessels ~60 mg/l
Sulfate
40 Vessels
1052 gpm
Product
~20 mg/l SO4
Water,
1458 gpm,
~40 mg/l SO4
Field development scaling potentials
with and without sulphate removal
Parameter mg/l Normal Seawater Formation Water Reduced-Sulphate
Seawater
Na+ 11130 18600 10050
K+ 430 750 350
Ca2+ 430 2600 275
Mg2+ 1350 300 630
Ba2+ 0.1 1100 0.1
Sr2+ 9.2 800 1.1

Cl- 20060 36400 18200

SO42- 2840 0 25
HCO3- 140 25 20

pH
7.9 6.09 7.9

Max. Downhole Scaling, mg/l

BaSO4 1300 40
SrSO4 490 0
CaSO4 0 0
CaCO3 73 34
Nanofiltration system CAPEX and OPEX
from Dow
Source, John McElhiney of Pratt Technology Management, April 2004

CAPEX(per bwpd capacity)

Facility cost (inc. installing) $44
Membrane Cost $16

Total Capex $60/bwpd

OPEX(per bbl water)
Chemicals $0.0080
Manpower for operating & cleaning $0.0006
Energy to operate $0.0176
Pre-membrane filter replacement $0.0011
Membrane replacement every 3 years $0.0220

Total Opex $0.0493/bbl

Therefore 100,000 bwpd LSSW (low sulphate seawater) for 15 years operation
Capex = $6m
Opex = $ 27 m ($4930/d x 365 x 15)
SRP in whole process
Brief history of nanofiltration for seawater

ƒWorldwide installations or being built now

9Marathon, Ewing Bank, GOM : 50,000 bwpd

9ChevronTexaco, Petronius Platform, GOM : 72,000 bwpd
9Total (Fina Elf), Girassol FPSO, WA : 400,000 bwpd
9Total, Dalia FPSO, WA : 265,000 bwpd
9Amerada Hess / Triton, Ceiba FPSO, WA : 135,000 bwpd
9Exxon Mobil, Kizomba A and B, FPSO, WA : 2 x 350,000
bwpd
9BP, Greater Plutonio, WA : 415,000 bwpd
9Petrobras, Roncador P52 FPU, Brazil : 300,000 bwpd
9Petrobras, Albacora Leste, Brazil : 220,000 bwpd

ƒLicenced suppliers of Dow / Marathon process

9Weir Westgarth, UK – Veolia France
9Natco (Axsia Serck Baker), USA / UK
9Kvaerner Process Systems, Norway
9US Filter (was part of Vivendi, became Veolia and in May 2004 sold to Siemens
of Germany)
Deareation
Deoxygenation (deaeration)

For Corrosion control

1. Chemical Means – 2Na2SO3 + O2 Æ 2Na2SO4

2. Physical means – reduce O2 partial pressure

ƒ Gas Stripping
ƒ Vacuum Stripping

Specification ? - Zero
- 5 ppb
- 10 ppb
- 20 ppb
- 50 ppb Strip Æ Zero by chemical
- 500 ppb Strip Æ Zero by chemical
Oxygen Removal

ƒ Combination of mechanical and chemical removal for

economic treatment.

ƒ Various types of “Towers” employed. E.g. Vacuum, Gas

stripper, Methanol oxidation (Minox™).

ƒ Chemical scavenger added to remove remaining oxygen

• Ammonium Bisulfite, Sodium Bisulfite

ƒ Residence time, pH and temperature important to provide

adequate reaction time.
Adverse Effects of Oxygen

¾ Accelerated general and pitting corrosion

¾ Accelerated bacterial growth

¾ Formation of solids
Oxygen Solubility In Brine

Oxygen Solubility in Brine

12

10
ppm Oxygen

0
0 50 100 150 200 250 300 350

3
ppm NaCl (x10 )
10C (50F) 20C (68F) 30C (86F) 40C (104F) 50C (122F)
Oxygen Scavenging

ƒ (NH4)HSO3 + O2 NH4+ + H+ + SO4-2

ƒ Sodium sulfite, sodium bisulfite, ammonium sulfite

and ammonium bisulfite all operate via the same
mechanism

ƒ Ammonium bisulfite, one of the more common

oxygen scavenging species shown in the example
above
Important Considerations

ƒ Concentration of the scavenger

– Treatment rate based on the ppm of oxygen in the
water and the activity of the scavenger

ƒ Rate of the reaction

– Fast enough to allow for complete reaction before
treatment with other chemicals or injection into the
system
– Typically reaction time less than 5 minutes
Rate of the reaction

• pH
• Temperature
• Catalysts
• H2S
• Other chemicals
Effects of pH

ƒ Oxygen scavenged with SO3-2 not with HSO3-

ƒ HSO3- = H+ + SO3-2

ƒ Need pH between 6-9 (optimum pH 7 – 9)

Catalysts

• Co+2
– Added to oxygen scavengers
• Ni+2
– Added to oxygen scavengers
• Fe+2
• Mn+2
• Cu+2
• High TDS waters have naturally occurring catalysts
Effect of Temperature

ƒ Rule of Thumb: The rate of reaction doubles for every

10oC

ƒ If it takes 5 minutes to scavenge water at 50oC (122oF), if

it cools to 40oC (104oF) it will take 10 minutes
Effects of H2S

ƒ 6 H+ +2S-2 + SO3-2 3So + 3H2O

ƒ H2S removes the catalysis by precipitation

ƒ Scavengers works best if H2S is below 5 ppm

Effects of Other Chemicals

ƒ Biocides
• Aldehydes forms salts, biocidal activity lost
• Quaternary Amines have no major interactions
• Oxidizing biocides (chlorine, hypochlorite, and chlorine
dioxide) react with the sulfites and bisulfites resulting in
loss of activity

ƒ Scale Inhibitors
• Depends on type of scale inhibitor, some have no
interaction while others are incompatible. Check with
supplier of scale inhibitor
Effects of Other Chemicals

ƒ Corrosion inhibitors
• Effect of inhibitors can vary, but can be
added after scavenging reaction is completed

ƒ Alcohols
• A major reduction in scavenging ability is
seen in the presence of alcohols
Oxygen Removal

ƒ Physical means – reduce O2 partial pressure

– Gas Stripping
– Vaccum Stripping

ƒ 2Na2SO3 + O2 Æ 2 Na2 SO4

Oxygen Removal
Interaction of Oxygen Scavengers
with Other Materials

ƒ Ammonium bisulfite is a reducing agent and will therefore react with

oxidizing agents. Reacts with residual chlorine – dose down stream of the
deaeration unit so that chlorine residual is removed. Dosing near the
chlorine injection point should be avoided as this will negate the oxygen
removal of the bisulfite and the biocidal effect of the hypochlorite.

ƒ Oxygen scavenger reacts with THPS and inactivates bisulfite

ƒ Bisulfite reacts with aldehydes (common biocide formulation ingredients).

The reaction product is a sticky plastic material that can easily block lines.
On no account should a system that has pumped aldehydes be used for
bisulfite without a thorough clean-out; or vice versa.

ƒ Avoid mixing bisulfite with acids or acid based cleaners. The reaction will
produce sulfur dioxide fumes that are a health risk.
Application Requirements

• Injection should be into a fast flowing stream that

will provide rapid mixing. An injection quill may be
used to facilitate mixing.
• Maximum residence time
• Higher temperatures
• Excess bisulfite
• Higher pH
• 100% availability
Monitoring Value

ƒ Monitoring Parameters
ƒ Monitoring Locations
ƒ Monitoring Frequency
ƒ Monitoring Techniques
ƒ Manpower Requirement
ƒ Trend analysis
Monitoring Program Value

• Monitoring concentrations or residuals

– Chlorine
– Oxygen Scavenger
– Dissolved Oxygen
– Iron count / LPR
– Turbidity
– MPN Bacteria
– Suspended Solids
• Through Filtrate
• Particle size analysis

• Monitoring effects
– Chlorine measure filtrate turbidity /particle counts
– Filter aid/s measure filtrate turbidity/particle counts
– Antifoam measure dissolved oxygen and corrosion rates
– Corrosion Inhibitor Iron count/LPR measure corrosion rates
– Oxygen Scavenger measure corrosion rates
– Scale inhibitor possibly turbidity/particle counts/suspended solids
– Biocide Bacteria/H2S/suspended solids/particle counts
Total Suspended Solids & SDI
Coulter Counter – Particle size distribution
Dissolved gases

ƒ Dissolved oxygen
– Raw water ~ 5-10 mg/l
– Injection water ~ 5-10 μg/l i.e. 99.9% removal
(if excess scavenger present, oxygen = zero μg/l)
ƒ Dissolved carbon dioxide
– Not of concern in seawater
ƒ Dissolved hydrogen sulphide
– Due to SRB only, in seawater system
Oxygen Control
Iron counts vs chemical treatment date
on wet well tubulars

Dissolved Iron (mg/l) Treatment Date

80
60
40
20
0
14/02/9 06/03/9 26/03/9 15/04/9 05/05/9 25/05/9 14/06/9 04/07/9 24/07/9
8 8 8 8 8 8 8 8 8
Chemetrics iron kit
Electrochemical corrosion
monitoring

Cormon Ceion Technology Portable LPR / ER equipment

an enhanced form of electrical resistance
Corrosion monitoring

Rohrback Cosasco systems

equivalent to Cormon’s
Ceion system is “Microcor”

Similarly, this is a form of

enhanced electrical
resistance
Common errors in monitoring

1. Insufficient facilities
Equipment, laboratory, consumables
2. Inadequate QA
Manuals, calibration procedures, calibration materials / equipment,
equipment servicing
3. Untrained chemical technicians (or no technicians!)
4. Motivation and / or supervision insufficient
5. Inappropriate monitoring programme - often irrelevant parameters
measured frequently, and important ones rarely or never
6. No review, evaluation and action taken on short-term and longer trend
data - by W.I. Team (chemical technicians, plant engineers, microbiologist,
corrosion engineer, etc)
Discussion