GB2244279A - Fluorosilicone anti-foam additive - Google Patents
Fluorosilicone anti-foam additive Download PDFInfo
- Publication number
- GB2244279A GB2244279A GB9110956A GB9110956A GB2244279A GB 2244279 A GB2244279 A GB 2244279A GB 9110956 A GB9110956 A GB 9110956A GB 9110956 A GB9110956 A GB 9110956A GB 2244279 A GB2244279 A GB 2244279A
- Authority
- GB
- United Kingdom
- Prior art keywords
- oil
- fluorosilicone
- water continuous
- continuous emulsion
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 21
- 239000000654 additive Substances 0.000 title claims abstract description 14
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- 239000003921 oil Substances 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 239000010779 crude oil Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 4
- -1 ethoxy sorbitan esters Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Colloid Chemistry (AREA)
- Lubricants (AREA)
Abstract
A water continuous emulsion suitable for use as an anti-foam additive comprises (a) 85-98% by weight of a fluorosilicone oil and (b) 2-15% by weight of an aqueous surfactant solution. The additive is suitable for use in the separation of crude oil containing associated gas into liquid oil and gas. The additive may be used in both aqueous and non-aqueous systems and allows fluorosilicone oils to be used without the need for environmentally damaging chlorofluorocarbons.
Description
FLUOROSILICONE ANTI-FOAM ADDITIVE
This invention relates to a fluorosilicone anti-foam additive, to a method for separating associated gas from crude oil involving the use of the additive and to a stabilised composition containing the same.
When oil is produced from a well, it is forced from the reservoir by pressure up the well to the surface. As the oil rises the pressure becomes less and gas associated with the oil is progressively released from solution.
After emerging from the well, it is usually necessary to treat the mixture of liquid oil and gas to remove free gas and also dissolved gas which is likely to come out of solution when the oil is maintained at about atmospheric pressure, for example, during transport in a tanker.
The separation may be effected near the well head or, alternatively, the oil and gas may be conveyed under high pressure in a pipeline to a different location where the oil and gas are separated.
Sometimes a stable foam is formed as the gas separates from the oil with the result that liquid oil may be lost in the gas stream and the separator ceases to function effectively. To overcome this problem it has been proposed that an anti-foam additive should be added to the crude oil.
One method of administering anti-foam additive is by the formation of emulsions in water or other suitable polar media. In this way a dispersion is formed which can easily be dispersed further in the crude oil.
Fluorosilicone oils are currently used to combat foaming in sour crude oils. Whilst they are stable in the presence of hydrogen sulphide the most efficient fluorosilicones suffer from the disadvantage that in their pure undiluted form they are very viscous materials which are too viscous for direct use.
Unfortunately they are not soluble in conventional solvents and current practice is to use them diluted with a chlorofluorocarbon (CFC). CFC's however are undesirable materials because of their toxicity and cost.
Fluorosilicone oils being insoluble in water should be able to form emulsions. However because of their high viscosity they are difficult to emulsify in water. The high viscosity ratio of the fluorosilicone oil to water favours the formation of water-in-oil emulsions instead of the more suitable oil-in-water emulsions. In the former situation the fluorosilicone oil is not in a dispersed state and the viscosity of the emulsion is higher than that of the fluorosilicone oil itself. In the case of an oil-in-water emulsion however the fluorosilicone oil would be in the form of small droplets and the resultant emulsion would have a viscosity very much lower than that of the fluorosilicone oil itself.
We have now found that fluorosilicone oils may be emulsified in water in the presence of water soluble surfactants to form stable emulsions suitable for use as anti-foam additives.
Thus according to the present invention there is provided a water continuous emulsion, suitable for use as an anti-foam additive comprising (a) 85-98Z (by wt) of a fluorosilicone oil and (b) 2-15X (by wt) of an aqueous surfactant solution.
The aqueous surfactant solution comprises 1-lOZ (by wt) of surfactant, preferably 7-10% (by wt).
Suitable fluorosilicone oils are of formula
wherein R1 is an alkyl or a phenyl radical,
R2 is the same as R1 or the radical CnF2n+1(CH2)20 in which
n = 4 - 16,
and x is in the range 5 to 100,
y is in the range 0 to 10,
and that a maximum of 90% of R2 is the same as R1.
The viscosity of the fluorosilicone oil varies from 400 to 1M cP at 25-C.
Suitable fluorosilicone oils are those disclosed in British patent specification 2196976.
Suitable surfactants may be either nonionic, cat ionic or anionic surfactants.
Suitable nonionic surfactants include alkyl ethoxylates, alcohol ethoxylates, ethoxy sorbitan esters, amine ethoxylates and alkyl phenyl ethoxylates.
Suitable cat ionic surfactants include quaternary ammonium salts for example cetyl trimethylammonium bromide.
Suitable anionic surfactants include sodium dodecyl sulphate, sodium dodecyl benzene sulphonate and sodium ether sulphonates.
Emulsions according to the present invention may be prepared by directly adding hot fluorosilicone oil to the aqueous surfactant solution, mixing being effected under low shear conditions.
The fluorosilicone oil is added preferably at a temperature in the range 60-80 C.
By low shear conditions we mean mixing at such a rate to produce low shear conditions in the range 10-1,000 preferably 50 to 250 reciprocal seconds.
Suitable mixers include blenders employing propellers, paddles etc or static mixers.
Emulsions according to the present invention are stable in storage.
As previously stated the emulsions of the present invention are suitable for use as anti-foam additives particularly for use in the degassing of crude oil.
Thus according to another aspect of the present invention there is provided a method for the degassing of crude oil containing associated gas into liquid oil and gas wherein the separation is carried out in the presence of a water continuous emulsion containing an effective amount of a fluorosilicone oil as hereinbefore described.
The fluorosilicone oil is suitably employed in amount 0.1 to 20 ppm expressed on the basis of active agent, a reference to the pure fluorosilicone oil in its undiluted state.
The emulsion of the present invention may be diluted to the required active level with clean water.
The emulsion is suitable for use in both aqueous and non-aqueous systems.
Emulsions according to the present invention are stable and can meet viscosity requirements eg a maximum viscosity for pumping of 1000 mPa.s.
Thus according to yet another aspect of the present invention there is provided a composition comprising degassed crude oil treated with a water continuous emulsion as hereinbefore described.
Emulsions of the present invention may also be suitable for use in the brewing, food processing and distillation industries.
The present invention is further illustrated with reference to the following Examples which describe both the preparation of emulsions and their effectiveness as anti-foam additives.
Example 1
The following emulsion was prepared in accordance with the present invention.
19g of a fluorosilicone oil as disclosed in British patent specification 2196976 and known as C2610 was added at 60eC to 0.5 g of a 10% aqueous solution of the surfactant NP20 (nonyl phenyl ethoxylate with 20 moles ethylene oxide). The mixture was emulsified for 30 seconds under low shear conditions using a mini laboratory stirrer operating at 1000 rpm.
The resultant oil-in-water emulsion was homogeneous and contained a mean droplet size of < 20 pm.
The emulsion was then diluted with water to a level suitable for application.
The anti-foam properties of the emulsions of the present invention were tested using the Bikerman gas sparging technique and by comparison with other anti-foam agents.
Example 2
3 ml of Emerald crude oil (North Sea) were placed in a calibrated thermostatted sintered glass tube of 1.5 cm diameter at 250C. Natural gas was sparged through the oil at a flow rate of 30 ml per minute to develop a foam. When the foam had stabilized its height and volume were recorded. The test was then repeated in the presence of an emulsion prepared according to Example 1. The concentration of active ingredient was 0.5 ppm.
The foaminess index (FI) was then calculated from the following relationship: FI (Secs) = volume of foam
gas flow rate
The lower the value obtained for FI the more effective the anti-foam agent is considered to be.
The anti-foam index (AFI) was then calculated from the following relationship:
AFI = FI (no antifoam agent) - FI (anti-foam aRent) FI (no -antifoam agent)
AFI = 1 indicates a perfect anti-foam agent
= 0 indicates no activity
= a negative value indicates a profoamer.
Examples 3 - 4
Example 2 was repeated using varying concentrations of active ingredient.
Examples 5 - 10
By way of comparison a series of tests were performed using
(a) a commercially available high molecular weight polydimethylsiloxane anti-foam agent known as SK 3527.
(b) a fluorosilicone oil as disclosed in British patent specification, 2196976 and known as C2610, supplied as a solution in the chlorofluorocarbon Frigane.
The results for Examples 2-10 are given in the accompanying table. For each example both the FI and AFI values were calculated.
From the results it is quite clear that the emulsions of the present invention are comparable with both the commercially available formulations as anti-foam agents. In addition the availability of such emulsions allows fluorosilicone oils to be used effectively in both aqueous and non-aqueous systems without the need for the environmentally damaging chlorofluorocarbons.
Claims (8)
1. A water continuous emulsion suitable for use as an antifoam additive comprising (a) 85-98X by weight of a fluorosilicone oil and (b) 2-15% by weight of an aqueous surfactant solution.
2. A water continuous emulsion according to claim 1 wherein the aqueous surfactant solution comprises 1-10% by weight of surfactant.
3. A water continuous emulsion according to claim 2 wherein the aqueous surfactant solution comprises 7-10% by weight of surfactant.
4. A water continuous emulsion according to any of the preceding claims wherein the fluorosilicone oil has the formula:
wherein R1 is an alkyl or a phenyl radical,
R2 is the same as R1 or the radical CnF2n+l(CH2)20 in which
n = 4 - 16,
and x is in the range 5 to 100,
y is in the range 0 to 10,
and that a maximum of 90% of R2 is the same as R1.
5. A water continuous emulsion according to any of the preceding claims wherein the surfactant is a nonionic surfactant.
6. A method for the degassing of crude oil containing associated oil and gas wherein the separation is carried out in the presence of a water continuous emulsion as hereinbefore described, said emulsion containing an effective amount of fluorosilicone oil.
7. A method according to claim 6 wherein the fluorosilicone oil is present in amount 0.1 to 20 ppm expressed on the basis of active ingredient.
8. A degassed crude oil treated with a water continuous emulsion as defined in any of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909011651A GB9011651D0 (en) | 1990-05-24 | 1990-05-24 | Anti-foam additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9110956D0 GB9110956D0 (en) | 1991-07-10 |
| GB2244279A true GB2244279A (en) | 1991-11-27 |
Family
ID=10676503
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB909011651A Pending GB9011651D0 (en) | 1990-05-24 | 1990-05-24 | Anti-foam additive |
| GB9110956A Withdrawn GB2244279A (en) | 1990-05-24 | 1991-05-21 | Fluorosilicone anti-foam additive |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB909011651A Pending GB9011651D0 (en) | 1990-05-24 | 1990-05-24 | Anti-foam additive |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9011651D0 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766513A (en) * | 1996-09-10 | 1998-06-16 | Exxon Research And Engineering Company | Antifoaming agents for lubricating oils (law455) |
| US5853617A (en) * | 1997-05-14 | 1998-12-29 | Gallagher; Christopher T. | Method and composition for suppressing oil-based foams |
| US6090758A (en) * | 1997-01-07 | 2000-07-18 | Exxon Research And Engineering Co. | Method for reducing foaming of lubricating oils |
| US6156808A (en) * | 1999-01-04 | 2000-12-05 | Halliburton Energy Services, Inc. | Defoaming compositions and methods |
| US6417142B1 (en) | 2001-10-02 | 2002-07-09 | Halliburton Energy Services, Inc. | Defoaming methods and compositions |
| US7273103B2 (en) | 2005-06-03 | 2007-09-25 | Halliburtoncenergy Services, Inc. | Cement compositions comprising environmentally compatible defoaming agents and methods of use |
| US7670423B2 (en) | 2005-06-03 | 2010-03-02 | Halliburton Energy Services, Inc. | Cement composition comprising environmentally compatible defoaming agents and methods of use |
| WO2015061868A1 (en) * | 2013-11-04 | 2015-05-07 | Dow Corning Do Brasil Limitada | Reduced foam petroleum composition field of the disclosure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2196976A (en) * | 1986-10-15 | 1988-05-11 | Goldschmidt Ag Th | Perfluoroalkylethyloxy-substituted siloxanes |
| GB2234978A (en) * | 1989-05-17 | 1991-02-20 | British Petroleum Co Plc | Fluorosilicone antifoam additive composition for use in crude oil separation |
-
1990
- 1990-05-24 GB GB909011651A patent/GB9011651D0/en active Pending
-
1991
- 1991-05-21 GB GB9110956A patent/GB2244279A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2196976A (en) * | 1986-10-15 | 1988-05-11 | Goldschmidt Ag Th | Perfluoroalkylethyloxy-substituted siloxanes |
| GB2234978A (en) * | 1989-05-17 | 1991-02-20 | British Petroleum Co Plc | Fluorosilicone antifoam additive composition for use in crude oil separation |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766513A (en) * | 1996-09-10 | 1998-06-16 | Exxon Research And Engineering Company | Antifoaming agents for lubricating oils (law455) |
| US6090758A (en) * | 1997-01-07 | 2000-07-18 | Exxon Research And Engineering Co. | Method for reducing foaming of lubricating oils |
| US5853617A (en) * | 1997-05-14 | 1998-12-29 | Gallagher; Christopher T. | Method and composition for suppressing oil-based foams |
| US6156808A (en) * | 1999-01-04 | 2000-12-05 | Halliburton Energy Services, Inc. | Defoaming compositions and methods |
| US6297202B1 (en) | 1999-01-04 | 2001-10-02 | Halliburton Energy Services, Inc. | Defoaming compositions and methods |
| US6417142B1 (en) | 2001-10-02 | 2002-07-09 | Halliburton Energy Services, Inc. | Defoaming methods and compositions |
| US7273103B2 (en) | 2005-06-03 | 2007-09-25 | Halliburtoncenergy Services, Inc. | Cement compositions comprising environmentally compatible defoaming agents and methods of use |
| US7670423B2 (en) | 2005-06-03 | 2010-03-02 | Halliburton Energy Services, Inc. | Cement composition comprising environmentally compatible defoaming agents and methods of use |
| WO2015061868A1 (en) * | 2013-11-04 | 2015-05-07 | Dow Corning Do Brasil Limitada | Reduced foam petroleum composition field of the disclosure |
| US10010813B2 (en) | 2013-11-04 | 2018-07-03 | Dow Brasil Sudeste Industrial Ltda | Reduced foam petroleum composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9011651D0 (en) | 1990-07-11 |
| GB9110956D0 (en) | 1991-07-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |