SPE/PS/CHOA 117176

PS2008-401

Successful Field Application of Novel, Non-Silicone Antifoam Chemistries

for High Foaming Heavy Oil Storage Tanks in Northern Alberta
Jonathan J Wylde SPE, Clariant Oil Services

Copyright 2008, SPE/PS/CHOA International Thermal Operations and Heavy Oil Symposium

This paper was prepared for presentation at the 2008 SPE International Thermal Operations and Heavy Oil Symposium held in Calgary, Alberta, Canada, 20–23 October 2008.

This paper was selected for presentation by an SPE/PS/CHOA Program Committee following review of information contained in a proposal submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers, the Petroleum Society of Canada, or the Canadian Heavy Oil Association and are subject to correction by the
author(s). The material, as presented, does not necessarily reflect any position of the SPE/PS/CHOA, its officers, or members. Papers presented at SPE, PS, and CHOA meetings are
subject to publication review by Editorial Committees of the SPE and PS. Electronic reproduction, distribution or storage of any part of this paper for commercial purposes without the written
consent of the SPE or PS is prohibited. Permission to reproduce in print is restricted to a proposal of not more than 300 words; illustrations may not be copied. The proposal must contain
conspicuous acknowledgement of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435 and
Editor, Journal of Canadian Petroleum Technology, Petroleum Society of Canada, Suite 425, 500 - 5th Avenue S.W., Calgary, AB, Canada T2P 3L5, fax 01-403-262-4792.

Abstract
Substantial foam formation was being experienced by two operators in several heavy oil leases in Northern Alberta. This 10 –
12 API crude had a large foaming potential and unique foam formation mechanism. Crude oil passed from the wellhead, via a
short flowline to a pair of hydrostatically balanced and heated storage tanks. The storage tanks heated the crude oil from
approximately 50°C to 85°C and in doing so, caused gas breakout and degassing which resulted in the formation of a thick,
persistent foam in the top of the tanks. The foam would enter the transportation trucks and end up at the local battery and
create carry over and separation problems in the process systems.

Silicone antifoam products were not acceptable due to both their poor environmental profile and also the influence these large
molecules had at the refinery where the crude oil was shipped for (predominantly) asphalt manufacture.

A wide range of chemistries were tested including phosphate based products, ethoxylated and propoxylated esters,
polyethylene glycol esters and oleates, alcohols, fatty alcohols and ethoxylated and propoxylated alcohols. One of the major
challenges detailed in this paper is that all products had to be freeze protected to -40°C. This was significant due to many
anti-freeze chemicals affect the efficacy of antifoam chemicals.

This paper details evolution of testing leading to the field application of this combined defoamer / antifoam chemistry. Initial
laboratory screening is included which describes a unique laboratory test method designed to mimic more accurately the
foam formation environment in the field. The paper goes onto illustrate the field trial evaluation as well as the case histories
of full field implementation of the highest efficacy products.

Introduction
Foam Background and Theory.

Crude oil is always associated with dissolved natural gas and in the reservoir this mixture behaves as a single liquid phase in
equilibrium with the reservoir conditions. As crude oil is produced through a system the pressure decreases and this causes
the liberation or degassing of the natural gas from the liquid phase. When this is combined with agitation, say for example
when passing through a downhole safety valve or choke, a dispersion of gas in the crude can be formed which is termed
foam1.

Idealized production would result in the removal of the gas from the crude in the process, for example in a separator, however
it is not normal for the gas phase to be totally removed – even after passing through three stages of the GOR of a crude oil
can be as high as 10 – 20 scf/bbl – and the residual foam causes operational challenges which can include:

• Liquid pump caviatation2.

• Black, smoky flares.
2 SPE/PS/CHOA 117176

• Liquid carry over in to the gas system3.

• Gas carry under into the oil and water system3.
• Reduction of separator capacity4.

Foams are colloidal systems where gas is the dispersed phase and the fundamental characteristic, which is common to all
irreversible colloids, is a very large interfacial area. A liquid foam can be defined as a two-phase system consisting of a three-
dimensional network of liquid lamellae that keep the enclosed gas particles discrete from one another. Foam stability can be
defined in terms of the strength and rheological properties of thin, liquid films, schematically depicted in Figure 1. Drainage
of liquid from the bulk foam phase occurs through the plateau borders and the liquid is drawn in to these regions by capillary
forces. The most important mechanism of crude oil foam stability has been proposed to be the film elasticity1.

Natural surfactants present in the crude oil, for example asphaltenes5 or short-chain carboxylic acids and phenols7, can also
stabilize foams by adsorption of a surface active compound at the gas-liquid interface which results in a lowering of the
surface tension. As the foam bubble walls drain of liquid a resistance to thinning occurs caused by the loss of natural
surfactant, therefore the surface tension increases. Surfactant migration occurs to compensate from a region of lower surface
tension to an area of higher surface tension thus resulting in restoration of film thickness. The foam is therefore stabilized and
this process is termed the film elasticity effect or the Marangoni effect and has been depicted in Figure 26.

Foam stability may also be enhanced by a viscosity effect either at the liquid surface or in the bulk phase, both of which
restrict film drainage. On the other hand, crude oil foam decreases in stability as the moisture content increases7.

Foam breakdown occurs via three generally accepted mechanisms:

• Film thinning: this is caused largely by gravity, thinning the top of the foam bubbles until the rigidity and strength of
the walls is reduced to a point where the foam bubble collapses.

• Redistribution of bubble sizes: if the gas bubble size is non-uniform and they contact one another then gas diffusion
can occur from the small bubbles to the larger bubbles because the gas pressure in the smaller bubbles is higher.

• Film rupture: when a foam bubble collapses the surface area of the droplets formed is significantly smaller than that
of the original bubble. Due to the very large energy differential, a droplet may reach speeds of 1000 cm.s-1 when a
bubble bursts. These particles can collide with nearby foam bubbles and in turn cause them to burst. A chain
reaction therefore occurs that can enhance the overall foam breakdown.

Foam Control Background and Theory.

Non-Chemical Foam Control.

Mechanical foam control focuses on the internal structures within production separators such as the orientation and type of
baffles, demisting pads and especially separator internals. Improvements to the inlet designs can improve plant efficacy. A
mechanical device can be installed on the separator inlet to enhance gas liquid separation and minimize the formation of foam
at the inlet of the separator. The device works by pre-separating the gas and liquid thus dissipating the momentum generated
at the inlet reducing the likelihood of foam formation. Several case histories are available in the literature that describe how
installation of process equipment has reduced the demand for chemical foam control methods3,8.

Chemical Foam Control.

Antifoams can be either defoamers, antifoamers or both. A defoaming agent might be regarded as a surface active agent that
increases the surface tension of a liquid5, 9. Antifoam agents controls the point at which the foam bubbles are nucleating in the
bulk phase, therefore the antifoam suppresses the formation of foam from the liquid phase. Most antifoaming agents are good
defoamers but conversely some defoaming agents are poor antifoams10. The ideal antifoam agent is totally insoluble in water
and has limited solubility in oil. It will also have a lower surface tension that the foaming medium, not be sensitive to
temperature and be resistant to chemical and oxidation attack. Furthermore it will have good dispersibility in the continuous
phase and have a low pour point11.

An antifoam will act by spreading over the gas liquid interface promoting rapid and local variations in the surface tension of
the foam bubbles. If the film elasticity is unable to resist these variations then the bubble will burst. Insolubility of antifoams
in crude oil is important because a product that is soluble in the crude oil will actually promote foam formation.
SPE/PS/CHOA 117176 3

There are many commercially available products for defoaming and antifoaming. Examples of several family types are
organic silicone and fluorosilicone compounds, phosphate esters, metallic soaps of fatty acids, sulfonated compounds,
amides, polyglycols, glycol ethers and alcohols12. By far the most common products in use are the silicone based products –
the term silicone is generic and covers all organosiloxane polymers, for example polydimethysiloxane (PDMS) or
poly(methyl-3,3,3-trifluoropropyl) siloxane, see Figure 3.

Non-silicone based antifoams are becoming more widely used in the oil industry, especially in drilling and cementing
applications. These types of antifoam have some advantages over silicone based products: they first and foremost (generally)
are much more biodegradable and therefore environmentally acceptable for certain oil producing basins, e.g. the North Sea.
More importantly to this study, non-silicone antifoams are much less likely to poison catalysts at refineries because they are
less persistent and thermally stable. The obvious disadvantage of non-silicone antifoams is that they are lower efficacy and
are more soluble in the oil product therefore are able to interact with the oil and other production chemicals.

Case History – Northern Alberta Crude Oil Storage Tanks

Background.

In Northern Alberta one operator of a lease comprising several hundred wells was experiencing production inhibiting foam
formation in the crude oil storage tanks. Typically the wells comprised a screw well pump lift system as the crude oil was
very heavy (10 – 12 API) with a high asphalt content (30 – 40%) and a relatively low GOR (c.10 scf/bbl). The produced
fluids pass through a flowline – typically 20 – 30 meters long – into a metering station and then terminated in a pair of
hydrostatically balanced and heated storage tanks. The storage tanks heated the crude oil from approximately 50°C to 85°C
and in doing so, caused large scale gas breakout and degassing which resulted in the formation of a thick, persistent foam in
the top of the tanks. The foam could enter the transportation trucks, ending up at the local battery thus creating carry over and
separation problems in the process systems. A photograph of a typical well site has been placed in Figure 4 and a schematic
in Figure 5. Any antifoam deployed in this system could not contain silicone based polymers because these compounds
poisoned the catalysts used in upgrading the crude oil and in the manufacture of asphalt.

There was a need to bring a step change in performance of the antifoam product. The previous incumbent products used
included a phosphate ester and a salted amine. The phosphate ester product itself was a good antifoam agent, however the
need to winterize the product to -40°C using chemicals such as methanol, butyl glycol ether etc. severely impeded the
defoaming and antifoaming properties. The salted amine performed well as an defoamer but as an antifoam injection rates as
high as 715 ppmv were required. The injection point was directly at the wellhead across from the flowline piping to the tanks.

Initial Laboratory Studies.

Initial screening of products was performed in the laboratory. Almost a dozen commercially available, non-silicone raw
materials were tested after being formulated into a freeze resistant matrix – either through addition of methanol, butyl glycol
ether, xylene, toluene etc.

The antifoam raw materials tested were:

1. Phosphate ester (incumbent 1)

2. Salted amine (incumbent 2)
3. Proprietary sulfonated salt
4. Ethanol, EGMBE and phosphate mixture
5. EO/PO adduct diester
6. PEG 300 diester
7. PEG 600 diester
8. PEG 400 diester
9. Dispersion of long chain fatty alcohols in water (17% solids)
10. EO/PO fatty alcohol adduct
11. Dispersion of long chain fatty alcohols in water (25% solids)

The as received crude oil would not create a significant foam in blank tests, therefore heptane was added to the crude oil to
simulate light (foaming) components in the crude and to artificially create a higher GOR – in all tests, 10% heptane was
sufficient to yield a representative foam on sparging. A 100 ml low form graduated cylinder was immersed in a water bath
made from a 1000 ml glass beaker. Heating was controlled via a power distributor with digital readout, an immersible heating
rod and thermocouples. The water bath was placed onto a stir plate and the whole assembly was secured with rods and
clamps. Nitrogen gas was introduced to the base of the low form beaker via a coarse sparge tube and flow was regulated
4 SPE/PS/CHOA 117176

through controlling the cylinder regulator and fine controlled using a gas flowmeter to ensure valid repeatability. A
photograph of the test equipment has been included in Figure 6.

The water bath beaker stirred constantly while being heated, then 40 ml of crude oil was poured into the 100 ml low form
graduated cylinder which was then clamped into place within the water bath. The sparge tube was inserted into the cylinder,
centered and clamped down. The thermocouple was then positioned into the oil and the oil heated up to 70°C. Once the oil
had achieved the desired temperature gas was flowed at 0.2 l.min-1 until a foam head formed up to the 70 – 100 ml level. This
level was maintained and recorded for 3 – 5 minutes. In order to test for defoaming properties, each chemical was injected at
specific concentrations by gently sweeping the pipette to the side. The timer was started and the foam drop recorded at 1
minute intervals until foam stopped dropping or maintained a level. The gas flow was then stopped and 5 minutes elapsed
until the gas was reapplied to observe return foam rate to test for antifoam properties.

All tests dosed in 400 ppmv for initial defoaming properties and the dose rate remained the same for subsequent antifoam
testing. The results have been displayed graphically in Figure 7. It can be seen from these results that both the incumbent
products did not perform well in the testing – incumbent 1 while showing some efficacy as a defoamer did not function at all
well as an antifoam agent. Incumbent 2 showed poor performance as both a defoamer and an antifoam at the test
concentrations used. Encouraging results were seen with blends 3 and 11 which were a sulfonated salt and fatty alchohol
respectively. The next stage of testing was to performance test the best products in the field in an onsite test that would not
need to add heptane to the crude oil to induce foaming.

Onsite Testing Studies.

The laboratory testing described above was valid to determine if a product was suitable for application in the crude oil, i.e.
suitably dispersible and compatible. These tests were performed on fresh, non-aged crude oil within minutes of removal from
the flowline sampling point, therefore precluding the requirement for addition of heptane.

Samples of crude were taken from specific wells and tested at a range of temperatures using an onsite water bath. Difficulties
in producing artificial foam were encountered using the conventional foam test equipment described above. Above a certain
temperature the gas simply escaped without producing a stable foam, and under that temperature the oil was simply too
viscous to work with, furthermore the viscosity and color of the oil made it impossible to read its volume in a graduated
cylinder and even to pour it. Due to these difficulties in producing the foam and measuring the volumes, a special procedure
was developed for testing the defoaming properties of the best laboratory performing products. Foam was produced with a
pressurized whip-cream cylinder using CO2 from Seltzer chargers. 500 ml of heated crude (45°C) was poured in the cylinder
and pressurized using one Seltzer charger, shaken, and kept warm on the water bath, as the ambient temperature was 6°C.
250 ml beakers were filled with foam and the test chemical added to the top of each beaker. After 10 minutes, the content of
the beakers was gently stirred and defoamer action was qualitatively estimated.

Of the products evaluated, blends 3 and 11 worked very well on the crude oil and showed superior performance to both the
incumbent chemistries. Blend 3 showed particularly good results with nearly instant action and no foam left after only a few
minutes upon addition of the chemical. All other chemicals tested were not as good as the incumbent prducts in terms of
defoaming action.

Due to the nature of this extremely heavy crude oil, a quantitative test was very challenging to perform – unlike in the
laboratory using idealized “live” crude – all results were qualitative only, i.e. ranked the products against one another. The
only way to make foam was by using compressed gas, mixed in a pressurized cylinder with the crude, the foam was formed
by forcing this mixture through a small orifice, thus allowing the production of approximately one liter of foam from 500 ml
of crude.

Field Application of Antifoam Chemicals.

Two chemicals were trialled in the field – blend 3 and blend 11. Two types of trial were performed: a defoamer application
that involved batch treating a 1 gallon pail of product through an application point directly into the storage tank; and
continuous injection into the flowline adjacent to the flowline to evaluate antifoam properties.

The proprietary sulfonated salt (blend 3) was trialled first and gave excellent defoaming when using 1 gallon batches. The
product performed successfully as an antifoam when injected at 200 – 250 ppm. The EO/PO fatty alcohol adduct (blend 11)
was trialled a few weeks later and defoaming performance was identical to that displayed by blend 3. When blend 11 was
used on continuous injection as an antifoam the performance was marginally superior to that of blend 3.

Work is now continuing to implement this foam mitigation chemical strategy field wide after the success of the initial trial.
SPE/PS/CHOA 117176 5

Conclusions

The initial laboratory testing showed:

• Inducing foam in heavy, aged crude was very challenging and required addition of heptane to artificially create the
foam.

• Both the incumbent antifoam products were poor performers and that blends 3 and 11 showed far more efficacy at
both defoaming and foam inhibition.

The follow up on site antifoam testing showed:

• That foam could be induced without the addition of heptane by using a Seltzer cylinder in a semi-quantitative
manner to rank performance of products against one another.

• Testing confirmed the initial laboratory testing insofar as blends 3 and 11 showed the best performance and were
superior to that of the incumebent products.

Field trials were successful using both blends 3 and 11 and field wide implementation is now being progressed, the final
choice of antifoam being dependent on supply chain, cost because performance of the two products was indistinguishable
during the field trials, both products performing very well at 200 – 250 ppm.

References

1. Callaghan I.C. and Neustadter E.L. (1981) Foaming Crude Oil: Study of Non-Aqueous Foam Stability. Chem. and Ind., 53 – 57.

2. Fallin S., Sharp S.P., and Wolfe J.L (1971) Defoaming Agents for Increased Oil Production Rates of Foamy Crudes – Laboratory
Screening Tests and Field Results. SPE 2841, Journal of Petroleum Technology, Volume 23, No. 2, 233 – 238.

3. Wylde J.J., Williams G.D.M. and Cousins R.E. (2005) Unlocking the Potential: A North Sea Heavy-Oil Success Story. SPE/PS-
CIM/CHOA Int. Thermal Operations and Heavy Oil Sym. Calgary, Alberta, Canada.

4. Cassani F., Ortega P., Dávila A., Rodriguez W., Lagoven S.A., and Serrano J. (1992) Evaluation of Foam Inhibitors at the
Jusepin Oil/Gas Separation Plant, El Furrial Field, Eastern Venezuela. SPE 23681, SPE Latin America Petroleum Engineering
Conference, Caracas, Venezuela.

5. Kouloheris A.P. (1970) Foam Destruction and Inhibition. Chemical Engineering, 77, 143 – 146.

6. Callaghan I.C., Gould C.M., Reid A.J., and Seaton D.H. (1985) Crude-Oil Foaming Problems at the Sullom Voe Terminal. SPE
12809, SPE Journal of Petroleum Technology, Volume 37, No. 12, 2211 – 2218.

7. Callaghan I.C., McKechnie A.L., Ray J.E., and Wainwright J.C. (1985) Identification of Crude Oil Components Responsible for
Foaming. SPE 12342, SPE Journal, Volume 25, No. 2, 171 – 175.

8. Chin R.W., Inlow H.L., Keja T., Hebert P.B., Bennett J.R., and Yin T.C. (1999) Chemical Defoamer Reduction with New
Internals in the Mars TLP Separators. SPE 56705, SPE Annual Technical Conference and Exhibition, Houston, Texas.

9. Garret, P. R. (1993) Defoaming: Theory and Industrial Applications, Marcel Dekker, New York.

10. Blute I., Jannsson M., Oh S.G., and Shah D.D. (1994) The Molecular Mechanism for Destabilization of Foams by Organic Ions.
J. Amer. Oil Chem. Soc., Volume 71, No. 1, 41-46.

11. McGhee J. (1989) Selecting Chemical Defoamers and Antifoams. Chemical Engineering, Volume 96, No. 4, 131-135.

12. Colbert J. C.(ed) (1981) Foam and Emulsion Control Agents and Processes: Recent Developments. Chemical Technology
Review, Number 188, 1 – 52. Noyes Data Corporation, Park Ridge, NJ.
6 SPE/PS/CHOA 117176

Figure 1: Idealized foam structure.

SPE/PS/CHOA 117176 7

6
Figure 2: Film elasticity (Marangoni effect) .
8 SPE/PS/CHOA 117176

Figure 3: Common antifoam product chemical formula and structure, upper is PDMS, lower is a
fluorosilicone polymer. In each case n = 0 to 2500.

Figure 4: Photograph of a typical well site.

SPE/PS/CHOA 117176 9

Figure 5: Schematic of a typical well site.

Figure 6: Laboratory screening test equipment.

10 SPE/PS/CHOA 117176

120 1
2
Defoamer Antifoam
Test Test 3
4
100
5
6
Foam Height (ml)

7
80 8
9
10
11
60

40

20

0
0 5 10 15 20 25
Time (minutes)
Figure 7: Results of initial lab screening tests.