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Comparative Study of Normal and Acid Demulsifiers in Treating Aged Crude

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Marfo SA, SF J Petroleum, 2018, 2:1

SciFed Journal of Petroleum

Research Article Open Access

Comparative Study of Normal and Acid Demulsifiers in Treating Aged

Crude Oil Emulsions

1
Ikpea E, 1Appah D, *2Marfo SA

1
University of Port Harcourt, Petroleum Engineering Department, Nigeria
*2
University of Mines and Technology, Petroleum Engineering Department, Ghana

Abstract
Mature oilfields present a myriad of challenges to the petroleum industry, and among these is emulsions
formation. Water-in-oil emulsion is a common and normal type of crude oil emulsion which occurs at many stages in
the production and treatment of crude oil. About two-thirds of petroleum production of every oil field exists in the form
of water-in-oil emulsion. The stability of these emulsions compounds its treatment and tends to result in accumulation
of aged and tight emulsions. Normal demulsifiers even at high treatment rates in combination with elevated temperature
are unable to completely break these emulsions. A more advanced demulsifier capable of breaking aged and tight
emulsions is therefore required. This paper focuses on comparing and investigating the effectiveness of demulsifiers
and organic acids in treating aged and tight emulsions. Series of laboratory tests were conducted using demulsifiers
and organic acids and combination of the two via bottle test to treat aged crude oil emulsions produced in the Niger
Delta Region of Nigeria. The results revealed that using the combination of demulsifiers and organic acids were more
effective than using the demulsifiers or the organic acids treatment alone. The experiment showed that the optimum
concentration needed for the combination of the acid and demulsifier ranges between 30 and 50 ppm, which resulted
in 14% to 58% water separation from the emulsion system.

Keywords demulsifiers is largely based on empirical approaches in an

Demulsifiers; Water in Oil Emulsions; Aged; attempt to get the effective one which can work in shorter
Organic Acid; Phasetreat; Bottle Test separation times and at smaller dosages [2]. Ojinnaka [3]
asserts that, emulsions of oil and water are one of many
Introduction problems directly associated with the petroleum industry,
Emulsion problems in crude oil productions
result in the demand for expensive emulsion separation *Corresponding author: Marfo SA, University of Mines and Technology,
equipment such as heater treaters, separators and coalescers Petroleum Engineering Department, Ghana. E-mail: [email protected];
Tel: +233 55 33 73 883
[1]. Hence, chemical demulsification is considered
suitable from both operational and economic point of view Received March 30, 2018; Accepted May 07, 2018; Published May 17,
to break the crude oil emulsion. A chemical agent typically 2018

acts on the interfacial film by either reacting chemically Citation: Ikpea E, et al. (2018) Comparative Study of Normal and Acid
with the polar crude oil components or by modifying the Demulsifiers in Treating Aged Crude Oil Emulsions. SF J Petroleum 2:1.
environment of the demulsification. Crude oil specificity Copyright: © 2018 Marfo SA. This is an open-access article distributed
has long been recognised and many demulsifier products under the terms of the Creative Commons Attribution License, which
are formulated as a mixture of agents in a career solvent permits unrestricted use, distribution, and reproduction in any medium,
provided the original author and source are credited.
to improve performance. The formulation of commercial

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in both oil-field production and refinery environments. head, chokes and valves [9]. Demulsification is necessary
Crude oil contains complex mixture of organic composite. in many practical applications such as the petroleum
Its composition can vary due to its reservoir’s place of industry, coating, painting, and waste water treatment in
origin, depth and age [4]. Emulsions have long been of environmental technology [10]. Destabilization of water-
great practical interest due to their widespread occurrence in-crude oil emulsion is carried out by using either of
in everyday life. They may be found in important areas such four or combined methods such as mechanical, chemical,
as food, cosmetics, pulp and paper, pharmaceutical and thermal, or electrical. Additional methods such as pH
agricultural industry [5]. Petroleum emulsions may not be adjustment, filtration, membrane separation and heat
as familiar but have a similar long-standing, widespread, treatment techniques, are also applicable [11]. Knowledge
and important occurrence in industry, where they are about the properties and characteristics of emulsions and
typically undesirable and can result in high pumping the mechanisms that occur during water coalescence
costs, pipeline corrosions, reduced throughput and special of water droplets are required in fast separation [12]. It
handling equipment. Emulsions may be encountered at all is known that increase in temperature (thermal method)
stages in the petroleum recovery and processing industry. above the paraffin melting point ranging between 50-65°C
During processing, pressure gradients over chokes and may completely destabilize an emulsion [13]. However,
valves introduce sufficiently high mechanical energy input the application of heat alone is rarely providing sufficient
(shear forces) to disperse water as droplets in the oil phase emulsion resolution. The most common method of
[6]. Emulsions form a special kind of colloidal system in demulsification in both oil-field and refinery applications
that the droplets often exceed the 1000 nm limited size. is the combination of heat and application of chemical
In the petroleum industry the usual emulsions encountered design to neutralise and eliminate the effects of emulsifying
are water droplets dispersed in the oil phase and termed as agents [1, 8, 11, 13, 14]. The separation rate of water-in-
water-in-oil emulsion [7]. oil emulsion is dependent on the type of demulsifier, the
Arnold [8] stated that, there are three main criteria emulsion stability, the temperature, the process vessel,
that are necessary for formation of crude oil emulsion: two the concentration, the process residence time and the
immiscible liquids must be brought in contact, surface mixing energy. The most common method of determining
active component must be present as the emulsifying agent, relative emulsion stability for lab-scale is the simple bottle
and sufficient mixing or agitating effect must be provided test. It is an empirical test in which varying amounts of
to disperse one liquid into another as droplets. Stability is potential demulsifiers are added into a series of tubes or
widely used to refer to the persistence of an emulsion in bottles containing sample of an emulsion to be broken.
the environment, and has been identified as an important After some specific time, the extent of phase separation
characteristic of water-in-oil emulsions. Some emulsions and appearance of the interface separating the phases
quickly decompose into separate oil and water phases once are noted. The optimisation of the amount and type of
removed from the sea surface, while more stable emulsions chemical employed, contributes to reduce the oil content in
can persist for days to years. Arnold [8] indicated that the the produced water offshore. The development and use of
viscosity of an emulsion is correlated with its stability. All environmentally friendlier chemicals is facilitated through
emulsions, perhaps with the exception of microemulsions, build-up of more fundamental knowledge concerning
are thermodynamically unstable but may be relatively the process involved in stabilising and breaking the
stable in kinetic sense [7]. An emulsion can be kinetically emulsions. The success of chemical demulsifying methods
stable with respect to coalescence but unstable with respect is dependent upon the following [8]:
to aggregation. Emulsion can be categorised into stable, 1. An adequate quantity of a properly selected chemical
unstable and meso-stable emulsions based on stability and must enter the emulsion.
operational definitions [8]. 2. Thorough mixing of the chemical in the emulsion must
Crude oil is found in the reservoir in association occur.
with gas and saline formation water. As the reservoir 3. Sufficient heat may be required to facilitate or fully
becomes depleted water is coproduced with oil. Wells now resolve an emulsion.
coproducing water with crude oil are steadily increasing; 4. Sufficient residence time must exist in treating vessels
these immiscible fluids are readily emulsified by the to permit settling of demulsified water droplets.
simultaneous action of shear and pressure drop at the well

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The stability of emulsions is largely affected by “black art”, which produces as many failures as successes
the nature of the interface/film and surfactant adsorption [13]. To ensure the high quality performance, a demulsifier
mechanisms [10]. The process of chemical demulsification should possess the required characteristics. It should be
of a water-in-crude oil emulsion involves the acceleration able to partition into the water phase; dissolve in the oil
of the coalescence as well as the film rupture process. There phase; and have sufficient concentration to ensure a high
are four types of demulsifiers that are used to break the enough diffusion flux to the interface, etc.
crude oil emulsion. They are anionic, cationic, nonionic and There are various commercial formulations
amphoteric. The most effective demulsifier formulations such as VX7079 Demulsifiers from ESSO, D1 and D2
are by the combination of all types of demulsifiers. The [9]. Bhattacharyya [9], identified that both D1 and D2
classification given is based on the chemical structure of completely demulsified an East Texas crude oil after
the hydrophilic group [15]. Anionics are used practically in 10 minutes by using 10 to 15 ppm of each demulsifiers
every type of detergents, which are the main application of formulation. The suitable temperatures considered for
demulsifiers. This is because they are easy to produce and demulsification process for lab scale are between 50 to
have low manufacturing cost. Anionics are manufactured 70 °C, which are similar to the actual refinery process
and used in greater volume compared to the all other types [13]. Tambe and Sharman [20], observed that oil-in-water
of demulsifiers [15]. The anionics have the advantage of emulsions are better at low pH value ranging between 4 to 6,
being high and stable foaming agents; however, they do while water-in-oil emulsions are favoured at high pH values
have the disadvantage of being sensitive to minerals and that are between pH of 8 to 10. Sjoblom [21], concluded
the presence of minerals in water (water hardness) or pH that at very high and low pH values, the emulsions seem to
changes. The effectiveness of any demulsifier added to be stable, while intermediate pH seems to cause instability.
treatment system is directly dependent upon its ability to The optimum pH values in treating crude oil emulsions are
make optimum contact with the emulsion. Therefore, the between 5 and 12. Gafonova [21] showed the influence
emulsion must be sufficiently agitated after the chemical of solvents of various aromatic and structure including
demulsifier has been added [16]. Recent laboratory and benzene, toluene, xylene, ethylbenzene, tert-butyl benzene
field experience have demonstrated the ability of some and cymene on emulsion stability. The results indicate that
dispersants to break emulsions formed at sea, particularly the more aromatic solvents (i.e., with the highest content
before the extremely viscous and stable “mousse” stage of the aromatic carbon) are more effective in destabilising
of emulsion forms. This demulsification activity promotes emulsions.
coalescence of the water droplets in the emulsion, which in Ese [12], observed that adding salts to the
turn causes separation of water and lowering of viscosity asphaltic emulsions cause the depletion force to reduce at
[17]. Demulsifiers are very similar to emulsifiers because low salt concentrations, leading to a melting aggregates,
both are surfactant in nature. whereas at high concentrations, rapid aggregation occurs
The history of chemical demulsifiers shows that as a consequence of van der Waals attractive force. The
prior to the knowledge of polyether condensates synthesis, salts ions lead to an increased relaxation of the film formed
chemicals such as Turkey red oil, sulphuric acid, sulphated and a decrease in the resistance to press ion compared to
castor oil, mahagony soaps, polyamines and polyhidric distilled water [23]. The investigation of the film formed
alcohols were used directly as demulsifiers [18]. With by the adsorption of asphaltene/resin mixture indicated
the production or formation of condensed polyether as a that resins start to predominate the film properties when
result of large-scale production of ethylene and propylene their content exceeds 40% [12]. The previous works have
oxides, a new class of nonionic detergents began to appear revealed that normal demulsifiers even at high treatment
[19]. The best polymeric surfactants used nowadays rates in combination with elevated temperature are unable to
throughout the world are alkoxylated material derivatives. completely break aged and tight emulsions [13]. Advanced
Because they are alkoxylated, they are considered as demulsifier capable of breaking aged and tight emulsions
non-ionic polymers. Among the disadvantages of having is therefore required. This paper focuses on comparative
organic solvents in a demulsifier formulation are increased and investigative study of the effectiveness of normal
cost, flammability, and toxicity. Finding a demulsifier demulsifiers and organic acids (Acetic) demulsifiers in
system that works well is often done by trial and error. treating aged and tight emulsions selected from the Niger
The selection process has historically been viewed as a Delta region of Nigeria.

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Materials and Method based on the screening process of demulsifiers using Odidi
Materials crude oil emulsion in Nigeria.
The materials used in this experiment are Comparative tests were done using different
classified into three groups that is the general chemicals, PHASETREAT (PT) separately and also combined with
the demulsifiers and the crude oil samples. These Acetic acid. PT 345) (Sludge breaker recommended for
chemicals were obtained from various suppliers such as BOGT), and PT 463 (Demulsifier in use at all SPDC Flow
acetone (>99.5%, from Mallinckrodt) as sterilise solvent; stations) on a sample of sludge from Tank 19. The sample
dichloromethane (100%, from Mallinckrodt) as solvent was collected after the tank had been settled. The results are
in resin recovery; silica gel (130-270 mesh, 60Å from presented in Tables 1 to 4 and the corresponding pictorial
Aldrich) and petroleum ether (40-60°C, from SureChem representation is shown in Figures 1 to 4 for PT 345, 463,
Products Ltd) were required for wax recovery; methyl 605 and 633 respectively. Regarding PT 345, without acid
alcohol anhydrous (99.9%, from Mallinckrodt), Toluene in the formulation, no separation of water was achieved.
(99.9%, from J.T Baker), benzene (from Fisher Chemical) This is an indication that the emulsion sample collected
and ethanol (from Clariant) were used as solvents to from the BOGT storage tank 19 was not compatible with
dissolve oil-soluble demulsifiers. Natrium Chloride the PT 345. However, when combined with the Acetic acid,
(above 99.5, from Merck KGaA) was used in preparation the optimal separation occurred at 10 ppm where 48% (at
of synthetic formation water. n-Decane and ethanol were 60 minutes) of water separation was achieved. Increasing
used in preparing synthetic oil which was used in single the acid concentration did not increase the volume of
emulsion preparation which is 70 %v/v n-Decane is mixed separated water.
with 30 %v/v ethanol. The demulsifiers used in this study PT 463 did not respond favourably to the emulsion
are methyl trioctyl ammonium chloride (PHASETREAT) as compared to PT 345. The highest water separation
and Acetic acid. occurred when 50 ppm (combined with acid) was used and
Crude oil samples obtained from Opuama, Odidi, this achieved water separation of 14% (at 60 minutes), and
Kolocreek, Imo River Agbada and Obigbo fields, Nigeria, when PT 463 was used unaided, only 6% of water separation
were used for this experiment. For the demulsifiers was achieved and this can be classified as unsatisfactory
screening, emulsions from Odidi’s field were used due results and incompatible with the emulsion system. For PT
to its high level of interfacial active fraction and stability. 605 at 40 ppm without acid, the optimal water separation
The other fields were used to test the efficiency of the was achieved and this occurred 60 minutes, recording
demulsifier formulation used in this study. All crude oil 54% water separation. It can be observed that PT 605 was
and oilfield brine samples were provided by ESSO (M) compatible and satisfactory with the emulsion system
Incorporated. when used unaided. This emulsion system does not require
a combined demulsifier and Acetic acid treatment, as the
Experimental Method highest or optimal water separation occurs when PT 605
This study was carried out by using two types of was used without acid (that is 54% within 60 minutes at
water-in-oil emulsions; actual and synthetic emulsions. 40 ppm concentration). The last phase treatment PT 633
Bottle test method was used in both single and composite shows that the optimal water separation is achievable at
demulsifiers screening in different concentration in order 60 minutes, with 58% water separation which occurred
to find the most effective demulsifiers. The formulation at 10 ppm (combined with acid). This phase treatment
obtained was tested by using Niger Delta’s (Nigeria) recorded the highest water separation among the four
crude oil and synthetic emulsions, and compared with phase treatment systems used in this study.
the commercial demulsifiers formulation. The detailed It was observed that, the demulsifiers that are
procedure adopted for the different stages of the bottle test efficient in water separation are inefficient in oil separation.
and results interpretation is outlined in Appendix A. This can be seen by the potential of methyl methacrylate and
butyl acrylate in both water and oil separation. According
Results and Discussion to the result obtained, the only demulsifier that is efficient
In this study the aim is to determine the most in both oil and water separations is Acetic acid. The water-
effective demulsifier for the emulsion systems without soluble demulsifier adsorb the water phase via oil phase.
considering the cost of formulation. The formulation was This causes film drainage and help in aggregation and

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Table 1: PT 345 and PT 345 + Acetic Acid

Sample: BOGT Storage Tank 19 Sludge
Date 6/8/2015
No Prod. Ratio, ppm 5 min 10 min 20 min 30 min 60 min
w w w w w
1 Blank - 0 0 0 0 0
2 PT 345 10 0 0 0 0 0
3 PT 345 20 0 0 0 0 0
4 PT 345 30 0 0 0 0 0
5 PT 345 + Acid 10 20 20 38 40 48
6 PT 345 + Acid 20 20 20 36 40 48
7 PT 345 + Acid 30 22 22 38 42 48
8 PT 345 + Acid 40 6 6 14 18 32
Note: w = water

Figure 1: PT 345 and PT 345 + Acetic Acid

Table 2: PT 463 and PT 463 + Acid

No Prod. Ratio, ppm 5 min 10 min 20 min 30 min 60 min

w w w w w
A Blank - 0 0 0 0 0
B PT 463 20 0 1 1 1 3
C PT 463 30 Tr 1 1 1 5
D PT 463 35 Tr 2 2 3 6
E PT 463 + Acid 40 Tr 3 3 4 6
F PT 463 + Acid 45 Tr 4 3 4 6
G PT 463 + Acid 50 2 8 8 9 14
H PT 463 + Acid 55 1 6 6 9 3
Note: w = water

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Figure 2: PT 463 and PT 463 + Acid

Table 3: PT 605 and PT 605 + Acid

Ratio,
No Prod. 5 min 10 min 20 min 30 min 60 min
ppm
w w w w w
1 Blank - 0 0 0 0 0
2 PT 605 35 2 2 2.5 3 3
3 PT 605 40 7 39 46 50 54
4 PT 605 45 4 28 42 48 54
5 PT 605 + Acid 50 4 20 40 44 50
6 PT 605 + Acid 55 4 20 40 44 50
Note: w = water

Figure 3: PT 605 and PT 605 + Acid

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Table 4: PT 633 and PT 633+ Acid

Ratio,
No Prod. 5 min 10 min 20 min 30 min 60 min
ppm
w w w w w
1 Blank blank Tr 0.5 1 1 3
2 PT 633 10 0.5 1 6 14 24
3 PT 633 20 Tr 0.5 4 10 18
4 PT 633+ Acid 10 0.5 1 26 54 58
5 PT 633+ Acid 20 3 8 24 42 57
6 PT 633+ Acid 30 1 1.5 10 24 56
7 PT 633 + Acid 40 1 1 10 24 54
Note: w = water

Figure 4: PT 633 and PT 633 + Acid

coalescence formation of the water phase. Based on the Delta, Nigeria. The following specific conclusions can be
above results, one can concluded that the water-soluble deduced:
demulsifiers such as methyl methacrylate, butyl acrylate 1. The results obtained shows that for PT 345 combined
and Acetic Acid are more efficient in breaking water-in-oil with Acetic acid at 10 ppm, 48% of water separation was
emulsion. achieved (within 60 minutes) which can be considered as
optimal and cost effective for Tank 19 sludge treatment.
Conclusions 2. PT 463 was incompatible and unsatisfactory with the
From the study, it can be affirmed that the bottle test emulsion system as less than 7% water separation was
method of demulsification is purely trial and error method, achieved when used both with and without Acetic Acid.
a ‘black art’. This was discovered in the results regarding 3. PT 605 was compatible with the emulsion systems when
the different Phasetreats and Acetic acid combined for used without Acetic acid. The optimal water separation of
breaking emulsions samples from selected from the Niger 54% was achieved using 40 ppm within 60 minutes.

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 Citation: Ikpea E, et al. (2018) Comparative Study of Normal and Acid Demulsifiers in Treating Aged Crude Oil Emulsions. SF J Petroleum 2:1.

4. PT 633 achieved optimal water separation of 58% when 10. Kim YH (1995) A Study of Dynamic Interfacial
it was combined with Acetic acid at a concentration of 10 Mechanisms for Demulsification of Water-In-Oil
ppm within 60 minutes. Emulsions. Ph.D. Thesis Illinois Institute of Technology.
Among the treatment methods employed in this
study, that is phasetreat with and without Acetic acid 11. Al Sabagh AM, Nasser NM, Khamis EA, et al. (2015)
combinations, (PT 633 + Acetic acid) recorded the most Resolution Of Water in Crude Oil Emulsion by some Novel
efficient water separation regardless of the cost. Aromatic Amine Polyester. Egypt J Pet 24: 363-374.

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Water-In-Oil Demulsifier. US Patent. in-Crude Oil Emulsions from the Norwegian Continental

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in the Stabilization of Water-In-Hydrocarbon Emulsions,
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Citation: Ikpea E, et al. (2018) Comparative Study of Normal and Acid

Demulsifiers in Treating Aged Crude Oil Emulsions. SF J Petroleum 2:1.

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Appendix A-1 Bottle Test Procedure 12. Fill small (15ml) graduated centrifuge tubes (graduation
1. Prepare solutions of all demulsifier samples to be marks in %) with gasoline. (100ml tubes are preferred for
examined (2% in solvent, xylene/IPA is suggested). Check accurate laboratory work but the 15ml tubes are better for
that solutions are clear. Label accordingly with demulsifier field use).
code.
13. Carefully pipette samples from the oil phase of each
2. Determine the approximate chemical concentration if sample and add to the half-filled centrifuge tubes. All the
unknown. Select a demulsifier believed to be effective. oil samples must be extracted from the same height within
Add 0.2ml to 3.0 ml of diluted demulsifier (from 2) and the oil phase and care should be taken to avoid extracting
follow steps 4, 6 through 18. The smallest amount of the water interface.
demulsifier that gives satisfactory results is the chemical
concentration that forms the basis of subsequent work. 14. Mildly agitate the oil / solvent mix by hand for 15
shakes to ensure thorough mixing. Centrifuge samples
3. Fill an appropriate number of 200ml graduated, for 2/3 minutes at approximately 1750 revs /min. Treat all
‘prescription’ bottles with emulsion (100ml). Substitute equally
150ml ‘milk’ test bottles if graduated bottles unavailable.
15. Read and record the basic sediment content (unresolved
4. Measure by pipette, aliquots of demulsifier solutions emulsion), water content and the sum of basic sediment
(from 2) into a corresponding sample of emulsion. The and water.
amount used should correspond to that determined from 3.
Label accordingly. 16. Add 2/3 drops of a dilute (2%) solution of a slugging
demulsifier (Treatolite F46 is an example) to each
5. Seal each bottle with a screw cap and agitate by hand for centrifuge tube, agitate by hand for a few minutes, heat
100 shakes at ambient temperature. Attempt to treat each to required temperature in a bath and re-centrifuge for 2
bottle equally. minutes.

6. Allow the sample bottles to settle. It may be possible to 17. Read and record the total basic sediment and water
separate the oil / water at ambient temperature. Bright oil content. Normally this will be all water. Compare with
and good water separation indicates a satisfactory result. value from step 16.

7. If step 6 does not indicate satisfactory results, loosen 18. At least one of the tested samples should have shown
caps, place bottles in a heated water bath at a temperature an acceptable result. If not longer temperature incubation,
representative of dehydration plant. agitation or settling time may be necessary and tests
will therefore be repeated. Alternative chemical may be
8. Remove bottles from bath, tighten caps and agitate by examined.
hand for 25 shakes. Again treat all samples equally.
19. In some instances, demulsifiers will show a sludging
9. Observe appearance after several minutes. Clear oil is a effect at the interface. Even ‘good’ products may do this
good sign. Cloudy, dull oil still contains water and is less if overdosed. Sludge should no longer be present by stage
good. 18.

10. Return sample bottles to water bath and allow to stand 20. As a precaution, pipette all coalesced water from bottles
for a longer period. Viscous crudes may require several deemed to be ‘acceptable’. Shake very gently 10 times and
hours before some separation occurs. quickly pour into centrifuge tubes half filled with gasoline,
agitate and centrifuge for 2 minutes.
11. Observe and record the amount of water separation in
each bottle. This result is only an indicator of performance 21. Record water and basic sediment content. Demulsifiers
and cannot be used alone to compare products giving lowest basic sediment content are to be preferred.

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 Citation: Ikpea E, et al. (2018) Comparative Study of Normal and Acid Demulsifiers in Treating Aged Crude Oil Emulsions. SF J Petroleum 2:1.

22. Step 17 may be repeated on centrifuged sample from

21. Optional.

23. It is normal to screen many demulsifiers. Several test

series will be undertaken to cover the full range. The better
products are then subject to a final selection test. If there is
a demulsifier currently in use in the field then this will be
used for comparison.

Appendix A-2 Interpretation of Results

1. Eliminate all products which did not resolve the
emulsion to distinct oil and water phases.

2. Eliminate products that gave significant basic sediment

in step 22.

3. Eliminate products that gave least satisfactory results in

step 16.

4. Further eliminate those products that showed significant

increase in basic sediment or water at step 18, compared
to step 16.

5. Preference should be given to sample showing the

lowest basic sediment in step 16.

6. Preference should also be given to products giving the

fastest coalescence / least sludging.

7. Compare costs for products that are equally effective.

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