OILFIELD REVERSE

DEMULSIFIER REV.01
BONY BUDIMAN
2021

https://www.linkedin.com/in/bony-budiman-39886031/
COMMON QUESTION

• What is emulsion oil in water, and what is the effect in

the oilfield ?
• What is reverse demulsifier?
• How to apply reverse demulsifier?
• Field cases !
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION
• FIELD CASES
• SUMMARY
OBJECTIVE

• Refresh simple definition of emulsion oil in water

• Sharing effect of oil in water at oil field
• Sharing reverse demulsifer mechanism
• Sharing some field cases
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION
• FIELD CASES
• SUMMARY
DEFINITION OF EMULSION

• A combination of two immiscible liquids which do not mix under

normal conditions
• Three conditions necessary to have an emulsion
• Liquids must be immiscible
• Sufficient agitation to disperse droplets of one liquid into the
other
• Presence of emulsifying agent or emulsifiers
 OIL IN WATER EMULSION (OIL CONTENT / OC)

Oil • Oil in water emulsion is condition when oil

Droplet
droplet dispersed in water phase
• Bear in mind that in oil in water emulsion the
oil is minor component (usually less than 1% or
Water 10,000 ppm) and the water is the major
Phase component.
• As emulsion, the oil may stay dispersed in water
phase for long period and cannot separate
instantly.
PROBLEM OF OIW EMULSION / OIL CONTENT

• Production loss
• Plugging especially at water injection well
• Environmental issue
PRODUCTION LOSS

• Glass bottle beside is produced water that contain 20 ppm oil content
• If the water production rate is 100,000 BWPD, lets calculate how
much volume of oil that discharged ?
• Volume of oil = concentration of oil content * water production rate
= (20 * 100,000 BWPD) / 106
= 2 BOPD = 318 LPD = 9,540 liters per month
• How if the oil content is 100 ppm ? The production loss will be 5
times higher
 PLUGGING

Oil Content and Flowability

700

600

500

400
time (s)

300

200

100

0
0 100 1000 5000 10000
Oil Content (ppm)
ENVIRONMENTAL ISSUE

• Overboard produced water will affect the

environment since oil is harmful to organism at
certain level.
• The specification of maximum oil content that
allow in overboard produced water vary from
maximum 15 ppm to maximum 50 ppm.
• In Indonesia the allowable limit for offshore is
max 50 ppm meanwhile for onshore is max 25
ppm
OUTLINE

• OBJECTIVE
• INTRODUCTION

• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION
• FIELD CASES
• SUMMARY
INDICATION OF OIL CONTENT
MONITORING

There are several methods available for both laboratory and field analysis of oil in water. The
choice of methods depends on budget, location of testing, time, and other factors. The most
important thing is to consistently test :
• Gravimetric
• Non gravimetric
• Spectrophotometer UV-Vis
• IR Absorbance
• Gas Chromatography –FID
• UV Fluorescence
• Quantum Cascade Laser Infrared (QCL-IR)
 GRAVIMETRIC

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SPECTROPHOTOMETER UV-VIS
INFRARED ANALYZER

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 GAS CHROMATOGRAPHY –
FLAME IONIZATION DETECTION (GC-FID)
• Principle : count amount of each component of hydrocarbon by column separation
• The method refer to ISO 9377-2 Water quality — Determination of hydrocarbon
oil index
• Sample to be acidified and extracted by hexane/pentane . The purified extract is
then injected into the GC. Once the GC column separates the different types of
hydrocarbons, each type is burned and detected by the Flame Ionization Detector
(FID).
• The sum of all the responses from each of the HC types is calculated in order to
determine the total oil in water. While
• GC-FID is a precise method for oil in water analysis, it is mainly suitable for lab use
due to the expense of the equipment and the need for technical users.

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 UV FLUORESCENCE

• UV fluorescence works by illuminating an oil in water sample with UV light. The

aromatic hydrocarbons in the sample emit fluorescent light that the instrument
can detect.
• The amount of oil in water in the sample is based on the intensity of the light
emitted.
• Because it does not require a solvent extraction, the technology is ideal for
online analysis of a wastewater stream.
• While UV fluorescence is a great technology for detecting aromatic
hydrocarbons, it will not detect any aliphatic compounds

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QUANTUM CASCADE LASER INFRARED (QCL-IR)

• QCL-IR measuring the CH3 absorption peak

located in the region 1350-1400 cm-1.
• The method works by first extracting and drying
the oil in water sample with cyclohexane or
cyclopentane. The extract is then measured on the
instrument and the intensity of the absorbance in
the region of 1350-1400 cm-1 is correlated to a
concentration value
 COMPARISON METHOD
No Method Advantages Disadvantage
1 Gravimetric • Simple equipment, • Time Consume
• Cheapest compared to others • Need huge sample volume
2 Spectrophotometer UV-VIS • Easy to use, Need specific calibration curve for each type
• Economic equipment of hydrocarbon
3 Infrared analyzer • Ideal for field use Does not detect volatile hydrocarbons
• Inexpensive solvents
4 Gas Chromatography – Precise and Provides details on • Equipment is expensive
Flame Ionization Detection different hydrocarbons • Requires trained personnel
present
5 UV Fluorescence Requires no solvent, Can be setup as an • Only detects aromatic hydrocarbons
online system in the field, Inexpensive • Does not follow any international method
6 Quantum Cascade • Does not require CFC solvent • Only detects CH3 compounds
Laser Infrared • Can be used in the lab or field. • More expensive than other types of IR
• Can measure TPH Separately Equipment
SAMPLING METHOD(8)

• Any water analysis method is only as good as the “sample” used to represent the
effluent stream.
• Sampling of a continuously flowing stream containing two or more phases (e.g.,
oil and water) is difficult unless the mixture is completely emulsified or is a very
fine stable dispersion.
• Generally, the larger the sample the more likely it is to be representative.
However, for practical reasons, the sample size varies from 100 ml to about 1l.
Typically, the smaller samples are used for daily analysis, whereas the larger
samples are used for monthly regulatory compliance purposes.
SAMPLING PROCEDURE(8)

• Flush the sample line thoroughly and take the sample quickly.
• Sample after a pump or a similar turbulent area where the stream is well mixed.
• Obtain the sample from a liquid-full vertical pipe, if possible.
• Use only glass or inert plastic (e.g., Teflon) stoppers. Cork or other absorbent materials must
not be used unless covered with aluminum foil.
• Do not rinse or overflow the bottle with the sample because an oil film will appear on the
bottle and give a false reading.
• Cap the sample and prepare a label immediately with an indelible, smear-proof marking pen.
Attach it to the bottle immediately.
• Analyze the entire sample and wash the bottle with solvent
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION
• FIELD CASES
• SUMMARY
IDEAL PROCESS OF OIL IN WATER TREATMENT

4
TREATING EQUIPMENT GROUPS

• Gravity Separators
• Wash Tank / Water Tank / Skim Tanks
• Corrugated Plate Interceptor
• API Separators
• Matrix Plate Coalescer (Performax)
• Dissolved Air Flotation
• Induced Gas Flotation
• Hydrocyclones
• Distillation
WASH TANK / SKIM TANK / WATER TANK
Corrugated Plate Interceptor (CPI)
API SEPARATOR
MATRIX PLATE COALESCER (PERFORMAX)

• The Performax Matrix Plate Coalescer is an

improved enhanced oil-water separator which
satisfies the oil producers' desire for a simple,
efficient separator.
• Results from light gravity paraffinic oils to
heavy gravity asphaltic oils are detailed.
• The configuration of the plates will force
hydrodynamic coalescence. The merging of
very small oil droplets into larger ones will
create extremely enhanced coalescence.
Rising oil droplets are captured by the next
higher plate
DISPERSED AIR FLOATATION (DAF)
DAF MECHANISM

Video Wemco / DAF

 INDUCED GAS FLOTATION

• The removal is achieved by injecting gas bubbles into the

wastewater in a flotation tank.
• The small bubbles adhere to the suspended matter causing the
suspended matter to float to the surface of the water where it may
then be removed by a skimming device, the next process is similar
with the Dispersed Air Floation
• The efficiency of IGF could be up to more than 95%. For example
if the inlet contain 100 ppm oil content, a good IGF (usually
combine with chemicals) could produce “clear” water that contain
no more than 5 ppm oil.

Courtesy Picture : https://en.citizendium.org/wiki/Induced_gas_flotation

HYDROCYCLONE
 DISTILLATION

• The mechanism takes advantage of the difference in boiling

points between water and oil.
• Since this is require high energy for heating, usually this is a
side process such as at MEG recovery unit.
• The inlet contain MEG, water and small amount of
hydrocarbon enter a heat vacuum reclaimer. The
hydrocarbon will be released first due to its lower boiling
Hydrocarbon point compare to water and MEG
• The effectiveness is very high that could produce oil
content below 5 ppm without addition of reverse
demulsifier

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OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION
• FIELD CASES
• SUMMARY
FOUR STAGES OF WATER CLARIFICATION

Stage 1: Coagulation • The oil in water separation process involves four stages :
coagulation  coalescence  flocculation  floatation

Stage 2: Coalescence • Coagulation - charge neutralization to bring oil droplets

close together
• Coalescence – small oil droplets merge into larger oil
droplets.

Stage 3: Flocculation • Flocculation – using chemical polymer to bring together

coagulated or coalesced particles into removable floc
• Flotation – used of induced gas to provide artificial lift for
Stage 4: Flotation
any of the above to the surface of the water
REVERSE DEMULSIFIER (RD)

• Chemicals used to improve the mechanical treatment called as reverse demulsifier or reverse
emulsion breaker, polyelectrolite or deoiler
• Reverse demulsifier accelerate the coagulation and coalescence process then the flocculation
and floatation process will be improved as well. Or in other words, the RD accelerate the oil
droplet join each others form higher oil molecule until it big enough to separate from water
phase due to differences in specific gravity
• By the mechanism, there are two type of RD :
• Flocculants : a nonionic polymer with high molecular weight (> 105)
• Coagulant : an ionic molecule with low molecular weight (<105)
• Organic coagulant
• Inorganic coagulant
MECHANISM OF FLOCCULANTS
FLOCCULANTS

1. Advantages
- Effectively separates uncharged particles such as soil and dust
- Low dosage, 1 – 10 ppm based on water rate.
- Rapid separation (<15 minutes)

2. Disadvantages
- May broken caused by high agitation
- Shall be well inversed, since it may become jelly if the water too little or separate if the
water is too much.
- Sensitive of over treat effect (effect that cause the separation not working well or even the
emulsion become tighter)
FLOCCULANTS APPLICATION

1. Direct concentrate injection (no dilution).

o This could be applied when the water is quite turbulence

2. Dilution injection
o The concentrate inverted with water until the concentration 1-1.5%. This solution may
stable less than 1 week. If found separation, the solution shall be re-mixing
o Use in line mixer, flocculants injected to a pre-dilution tank with a mixer prior to inject to
the wastewater.
 INVERSION

Before inversion After

inversi

Water Inversion Oil

phase phase

Oil Water
phase phase
ORGANIC COAGULANT MECHANISM
INORGANIC COAGULANT MECHANISM

FeCl3 AlCl3

Fe(OH)Al(OH)
3 3
COAGULANT

1. Advantages
- More resist to agitation.
- Well diluted at any proportion with water

2. Disadvantages
- May not too effective to separate waste water that contain a lot of suspended solid
- Not effective for relatively heavy crude oil
 COAGULANT VS FLOCCULANTS

No Parameter Flocculants Coagulant

1 Solubility in water Has specific solubility, usually at 1-1.5 % Well soluble
2 Aggitation Effect Sensitive Resistant
Suitable to separate light
Suitable to separate heavy oil and water with
3 Application to medium oil in water
suspended solid
emulsion
4 Work Mechanism Works as glue that sticks to oil droplets Charge neutralization
Before separator that
Before separator that contain relatively low oil
5 Injection Point content at any variation
content (for example below 200 ppm)
of content
Require low shear and
6 System Requirements Usually used in high shear system
settling time.
7 Selection Test Bottle Test Jar Test
Video Coagulation - Flocculation
SOME REVERSE DEMULSIFIER

COAGULANTS FLOCCULANTS
Aluminum Sulfate (Alum) Charged polyamides
Aluminum chloride (pH dependent) Polyanionics
Polyaluminum chloride (pH dependent) Polyampholytes
Zinc Chloride Polymeric surfactants
Sodium aluminate
Iron salts – (Iron chloride, Iron sulfate)
Polyferric sulfate
Mineral acids
REVERSE DEMULSIFIER SELECTION

• Bottle Test
• Used to evaluate coagulants
• Jar Test
• Used to evaluate flocculants
• Mini WEMCO™ Test
• Used to simulate induced gas flotation units, both mechanical and
hydraulic
• Soluble Organics Test
• To determine product and amount needed to meet produced
water discharge requirements
BOTTLE TEST
TEST PROCEDURES — BOTTLE TEST

• Make up 1% solutions of test chemicals including the

incumbent.
• Catch chemical-free representative sample.
• Pour agitated sample into 6 oz. Prescription bottles -
usually 6 bottles at a time - pour up 100 mL.
• Dose bottles.
• Give bottles 15-2000 slow rolls and rate immediately
(visually).
TEST PROCEDURES — BOTTLE TEST

• Shake bottles to simulate fluid flow (survey) and visually

rate. Record information.
• Do this for ratio test, screening test, and conformation test.
• Select product with best water and tight, well-coalesced oil
layers - oil must have bright “sheen” indicating treatment.
 JAR TEST

• The test refer to ASTM D2035 Coagulation

Flocculation Jar Test of Water
• Jar test is a pilot-scale laboratory test that simulates
flocculation with differing chemical types/doses.
• The purpose of the jar test is to estimate the
minimum dose required to achieve certain water
quality goals.
• Jar tests are conducted on a four- or six-place gang
stirrer, which can be utilized to simulate mixing and
settling conditions in a clarifier.

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 TEST PROCEDURES — JAR TEST

• Obtain fresh chemical-free representative sample.

• Fill jars to 800 mL level.
• Turn on jar test apparatus and dose jars with chemical
(dose based on 800 mL sample) while on very low speed.
• Mix jars at high speed (200 rpm) for 1 minute.
• Slow stirrers to 30 rpm and mix for 5 minutes.
 TEST PROCEDURES — JAR TEST

• Stop mixing and let jars stand for 1 minute.

• Rate jars for water clarity and floc size.
• Run ratio, screening, and conformation test as in
bottle tests.
• Record all observed data.
• Take sample of water about one inch from bottom
of jars and run turbidity or oil parts.
• Parameters using Jar Test are as per picture beside

Courtesy picture : ASTM D2035 Coagulation Flocculation Jar Test of Water

 MINI WEMCO TM TEST

• Wemco TM is a one of manufacture of floatation unit

• Mini Wemco is a test that mimic the principle of induced gas floatation
(IGF)
• The air induced to the chamber that contain waste water using a
motor, create a bubble air that help to float the oil droplet to the
surface.
• Reverse demulsifier added to the chamber and the performance
evaluated by the clarity of water after 1-2 minutes
• The test require 2 – 3 liters sample for each test. Relatively high
compare to bottle test or jar test that require 100-200 ml per test.

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TEST PROCEDURES — MINI WEMCO™ TEST

• Obtain fresh chemical-free representative sample.

• Fill WEMCO cell with chemical (you may want to screen products by
bottle tests).
• Start and run WEMCO for 1-2 minute - note rate of oil/solids removal.
• Stop WEMCO and let stand quiet for 1 minute.
• Take sample of water from bottom of cell.
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION

• FIELD CASES
• SUMMARY
 1. SYNERGY BETWEEN MECHANICAL AND CHEMICAL

OC = > 10,000
1 ppm

OC = 900 ppm

OC = 150 ppm

Deoiler OC = > 10,000

2 ppm

OC = 900 ppm

OC == 150
OC < 20ppm
ppm
 2. COAGULANT AND FLOCCULANTS COMBINATION

Well
D#17
Floc = 11
GPD

Gathering Station (GS)

Charlie

Well OC = 300 – 500 ppm

K#05
 2. COAGULANT AND FLOCCULANTS COMBINATION

Well
D#17 Coag = 7
GPD
Floc = 4
GPD

Gathering Station (GS)

Charlie

Well OC = 200 –
K#05 300 ppm
 2. COAGULANT AND FLOCCULANTS COMBINATION

Well
D#17
Coag = 4
GPD

Floc = 1
GPD

Coag = 4 Gathering Station (GS)

GPD Charlie

Well OC = 80 – 100
K#05 ppm
 3. INVERSION

Flocculants 100%,
Rate = 1 GPD
OC > 100 ppm
 3. INVERSION

Flocculants 1.5%,
Rate = 20 GPD
OC < 25 ppm
 4. OIL RECOVERY

• This salt water injection plant, located southwest of

Mendoza, Argentina, was designed to utilize two water
separation / retention tanks to provide acceptable wa-
ter quality for injection.
• One of the tanks was shut-in for reparation which was
projected to take 10 months to complete.
• This overburdened the system and reduced the
retention time by half, resulting in water with high oil-
in-water content, averaging 140 ppm

Courtesy picture : CS1570EN oil & gas producer recovers additional 117 barrels of oil per month and reduces oil-in-water content by 93% with SUEZ ProSolv* water clarifier
 4. OIL RECOVERY

• Initial treatment rates of 5 ppm were re-duced to 3

ppm during the test period.
• Oil-in-water in the system with one retention tank was
reduced from 140 ppm to 10 ppm( 93% reduction).
• In addition, filter changing frequency was reduced from
two changes per month (with two retention tanks) to
once per month (with one retention tank
• The single tank retention system was able to process
4600 m3/day of produced water

Courtesy picture : CS1570EN oil & gas producer recovers additional 117 barrels of oil per month and reduces oil-in-water content by 93% with SUEZ ProSolv* water clarifier
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• REVERSE DEMULSIFIER APPLICATION

• FIELD CASES

• SUMMARY
SUMMARY

• RD used to improve the oil in water separation in term of quality and

time due to limitation of mechanical process
• RD injected continuously at dosage (typically) 1 – 20 ppm based on water.
• The laboratory selection shall be conducted prior to field trial to
determine type and estimate dosage.
• The injection method shall be consider the field condition such as
mechanical facilities and production rate
REFERENCES

1. API Recommended Practice for Analysis of Oilfield Waters, RP 45, Third Edition, August
1998.
2. Production Chemicals for the Oil and Gas Industry, Malcolm A. Kellands Second Edition,
CRC Press, 2014
3. Oilfield Production and Microbilogy, HTS Consultant, 2007
4. Techniques for Measuring Oil in Water, Spectro Scientific, 2016
5. https://en.wikipedia.org/wiki/Dissolved_air_flotation
6. ASTM D2035 Coagulation Flocculation Jar Test of Water
7. Applied Water Technology, Charles C. Patton, C. C. Patton & Associates, Inc., Dallas, Texas,
1986
8. Produced Water Treatment & Injection, Yasser Kassem,