CA1155363A - Use of quaternized polyalkylene polyamines as demulsifiers - Google Patents
Use of quaternized polyalkylene polyamines as demulsifiersInfo
- Publication number
- CA1155363A CA1155363A CA000391599A CA391599A CA1155363A CA 1155363 A CA1155363 A CA 1155363A CA 000391599 A CA000391599 A CA 000391599A CA 391599 A CA391599 A CA 391599A CA 1155363 A CA1155363 A CA 1155363A
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- Prior art keywords
- oil
- emulsions
- water
- emulsion
- polyamine
- 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.)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Emulsions of oil and water are broken by contacting the emulsions with a quaternized polyalkylene polyamine, e.g., the adduct of 2-hydroxy-3-chloropropyl trimethyl ammonium chloride and a polyethylene polyamine.
29,821-F
Emulsions of oil and water are broken by contacting the emulsions with a quaternized polyalkylene polyamine, e.g., the adduct of 2-hydroxy-3-chloropropyl trimethyl ammonium chloride and a polyethylene polyamine.
29,821-F
Description
115$363 USE OF QUATERNIZED POLYALKYLENE
POLYAMINES AS DEMULSIFIERS
This invention relates to the use of quater-nized polyamines in the preventing, breaking or resolv-ing of emulsions of the water-in-oil type as well as oil-in-water type emulsions.
Most naturally occurring emulsions of petro-leum oil and water take the form of water-in-oil emul-sions in which the oil is a continuous phase and tiny drops o water are dispersed in the oil. Occasionally, however, oil-in-water emulsions are often encountered either in the production, handling or refining of petroleum oil or fractions thereof. Unfortunately, in both cases the emulsions are often extremely stable and will not resolve after standing for long periods.
While such emulsions often occur naturally, such emul-sions may also occur artificially resulting from one ormore of numerous operations encountered in various industries. For example, such emulsions may be obtained from producing wells as a result of enhanced oil recovery methods or from the bottom of crude oil storage tanks. Other such oil-in-water emulsions include steam cylinder emulsions, wax-hexane-water 29,821-F -l-emulsions, butadiene-tar-in-water emulsions, emulsions of flux oil and steam condensate, styrene-in-water emulsions and synthetic latex-in-water emulsions. In all instances, it is generally desirable to resolve the emulsion in order that the oil phase may be separated from the water phase.
Historically, such emulsions have been resolved or broken by contacting the emulsion with a chemical demulsifying agent thereby causing the emul-sions to resolve and stratify into its component phasesof water and oil or brine and oil after the emulsion has been allowed to stand in a relatively guiescent state. In another type of demulsification, the emul-sion contains substantial quantities of salt in the aqueous phase and it is necessary to carry out a desalting operation prior to further refinement of the oil phase in order to prevent the accumulation of large deposits of salt in the refining apparatus. In such desalting operations, it is common to employ a chemical demulsifying agent in a manner similar hereinbefore. A
wide variety of chemical demulsifying agents has been employed in this manner in the past. For example, such demulsifying agents include oxyalkylated condensation products obtained by reacting phenols, formaldehydes and alkylene polyamines as disclosed in U.S. Patent No. 3,166,516; ultra high molecular weight ethylen-ically unsaturated polymers, polyalkylene oxylene polymers, polyesters, polyamides and polymer of ketenes as described in U.S. Patent No. 3,557,017; aminoamido polymers as described in U.S. Patent No. 3,528,928; as well as other chemicals such as sulfonates, oxyalky-lated amines, oxyalkylated alkylphenols and oxyalky-lated alcohols. While each of the foregoing and other 29,821-F -2-1 ~55363 conventional demulsifiers are effective in some emul-sions, it is found that many are not as effective as desired, particularly in resolving emulsions derived from steam recovery of heavy crudes by processes typical of some of the California oil fields.
Accordingly, it is highly desirable to pro-vide a demulsification process for resolving emulsions of such heavy crudes as well as other water-in-oil emulsions and the like.
The present invention is such a demulsifi-cation method which comprises contacting an emulsion of oil and water with a demulsifying amount of a quater-nized polyalkylene polyamine which is an adduct of a halohydroxyalkyl quaternary ammonium compound and a lS polyalkylene polyamine.
While the demulsification method of the present invention is particularly effective in resolv-ing emulsions of water in heavy crudes as are commonly recovered from the California oil fields, such demulsi-fication method is also effective for resolving otheremulsions of oil-in-water and water-in-oil.
Emulsions of oil-in-water that are most effectively resolved by the method of this invention are oil field emulsions containing relatively small proportions of crude petroleum oil dispersed in water or brine and are hereinafter characterized as oil-in-water emulsions. Other such oil-in-water emulsions include emulsions in which traces of lubricating oil are found dispersed in steam from steam engines and 29,821-F -3-steam pumps often called steam-cylinder emulsions;
emulsions encountered in the waxing operations in oil refining, often called wax-hexane-water emulsions;
emulsions of flux oil in steam condensate produced in the catalytic dehydrogenation of butylene to produce butadiene; styrene-in-water emulsions and emulsions generated by sewage disposal operations. Although not as preferably resolved as the oil-in-water emulsions, water-in-oil emulsions are suitably treated by the method of this invention. Such water-in-oil emulsions are generally those naturally occurring emulsions of water and petroleum oil wherein the continuous oil phase has tiny droplets of water dispersed therein.
The preferred oil-in-water emulsions may contain widely different proportions of dispersed phase, for example, the oii field emulsions may carry crude oil in proportions varying from a few parts per million to 40 weight percent or higher in rare cases.
All of such emulsions are suitably treated in the practice of this invention, most preferably, however, such oil-in-water emulsions contain from 0.01 to 30 weight percent of oil based on the weight of the emul-sions. Also, while the method of the present invention is effective in treating emulsions derived from light crudes, the method is most effective in treating emul-sions of somewhat heavier crudes wherein the crude has a specific gravity in the range from 0.8 to 0.97 gram/milliliter.
The quaternized polyalkylene polyamines employed in the present invention are adducts of poly-alkylene polyamines and a halohydroxyalkyl quaternary 29,821-F -4-ammonium compound. Exemplary polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylene-tetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, 1-aminoethylpiperazyl diethylene-triamine, 1-aminoethylpiperazyl triethylenetetramine, propylenediamine, dipropylenetriamine, butylenediamine, aminoethylpropylenediamine and other polyamines having at least one primary amino group separated from another primary amino or secondary amino group by 2 to 4 carbon atoms. Of these polyalkylene polyamines, the higher molecular weight polyethylene polyamines and polypropy-lene amines such as those having a number average of 100 to 15,000 are preferred. Of particular interest are the polyalkylene polyamines that are cross-linked with ethylene dichloride as well as mixtures of such cross-linked polyamines with other polyalkylene poly-amines as mentioned hereinbefore.
Reacted with this polyalkylene polyamine is a halohydroxyalkyl quaternary ammonium salt. Examples of such quaternary ammonium salts include 2-hydroxy-3-chloropropyl trimethylammonium chloride, and similar hydroxyhaloalkyl trialkyl ammonium and other halo-hydroxyalkyltrialkyl ammonium halides with 2-hydroxy--3-chloropropyltrimethylammonium chloride being pre-ferred. The adduct of the polyalkylene polyamine andquaternary ammonium salt is advantageously prepared by adding the ~uaternary ammonium salt to the polyalkylene polyamine at ambient temperature. The mixture is then adjusted to alkaline conditions, e.g., pH = 8, by the addition of an aqueous solution of sodium hydroxide or other strong base. The resulting mixture is then heated, e.g., to 90C for 8 hours, until the reaction is completed. While the ratio of the quaternary salt 29,821-F -5-to polyalkylene polyamine in the adduct is not particu-larly critical, it is generally desirable that the molar ratio of quaternary ammonium moiety to amino moiety in the polyalkylene polyamine be in the range from 0.01:1 to 0.8:1, preferably from 0.05:1 to 0.8:1.
In the practice of this invention, the emul-sion to be resolved is contacted with an amount of the adduct which is effective to cause the emulsion to separate into two essentially distinct phases upon standing. Generally, such an amount will be in the range from 1 to 1,000 weight parts of the adduct per million weight parts (ppm) of the emulsion, preferably from 10 to 100 ppm.
The following examples are given to further illustrate the detailed practice of the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
ExamPle 1 To 100 grams of an oil-in-water emulsion containing 10 weight percent of crude oil having a specific gravity of 0.8 g/ml was added 2.4 parts per million based on the emulsion of the reaction product of 1 equivalent of N-~3-chloro-2-hydroxypropyl)-trimethyl ammonium chloride and 1 equivalent of poly-ethylene polyamine having a number average molecular weight of 324. The emulsion was then shaken for 5 minutes to effectively disperse the adduct into the emulsion. Thereafter, the emulsion was allowed to stand for 4 hours after which time the phases separated 29,821-F -6-such that each phase was essentially free of dispersed droplets of the other phase. In a similar manner, different samples of the same emulsion were contacted with different amounts of adducts within the scope of this invention and evaluated for demulsification efficiency. The results of these evaluations are recorded in Table I.
For purposes of comparison, a conventional polyalkylene polyamine demulsifier was similarly added to different samples of the aforementioned emulsion and evaluated for demulsification efficiency. The results of these evaluations are also recorded in Table I.
29,821-F -7-TABLE I
Demulsifying Sample Aqent (1) Demulsification No. TYPeAmount, PPm EfficiencY (2) Cl* Polyamine2.4 3 C2* Polyamine12.2 3 C3* Polyamine24.5 3 l 10% Quat 2.4 4
POLYAMINES AS DEMULSIFIERS
This invention relates to the use of quater-nized polyamines in the preventing, breaking or resolv-ing of emulsions of the water-in-oil type as well as oil-in-water type emulsions.
Most naturally occurring emulsions of petro-leum oil and water take the form of water-in-oil emul-sions in which the oil is a continuous phase and tiny drops o water are dispersed in the oil. Occasionally, however, oil-in-water emulsions are often encountered either in the production, handling or refining of petroleum oil or fractions thereof. Unfortunately, in both cases the emulsions are often extremely stable and will not resolve after standing for long periods.
While such emulsions often occur naturally, such emul-sions may also occur artificially resulting from one ormore of numerous operations encountered in various industries. For example, such emulsions may be obtained from producing wells as a result of enhanced oil recovery methods or from the bottom of crude oil storage tanks. Other such oil-in-water emulsions include steam cylinder emulsions, wax-hexane-water 29,821-F -l-emulsions, butadiene-tar-in-water emulsions, emulsions of flux oil and steam condensate, styrene-in-water emulsions and synthetic latex-in-water emulsions. In all instances, it is generally desirable to resolve the emulsion in order that the oil phase may be separated from the water phase.
Historically, such emulsions have been resolved or broken by contacting the emulsion with a chemical demulsifying agent thereby causing the emul-sions to resolve and stratify into its component phasesof water and oil or brine and oil after the emulsion has been allowed to stand in a relatively guiescent state. In another type of demulsification, the emul-sion contains substantial quantities of salt in the aqueous phase and it is necessary to carry out a desalting operation prior to further refinement of the oil phase in order to prevent the accumulation of large deposits of salt in the refining apparatus. In such desalting operations, it is common to employ a chemical demulsifying agent in a manner similar hereinbefore. A
wide variety of chemical demulsifying agents has been employed in this manner in the past. For example, such demulsifying agents include oxyalkylated condensation products obtained by reacting phenols, formaldehydes and alkylene polyamines as disclosed in U.S. Patent No. 3,166,516; ultra high molecular weight ethylen-ically unsaturated polymers, polyalkylene oxylene polymers, polyesters, polyamides and polymer of ketenes as described in U.S. Patent No. 3,557,017; aminoamido polymers as described in U.S. Patent No. 3,528,928; as well as other chemicals such as sulfonates, oxyalky-lated amines, oxyalkylated alkylphenols and oxyalky-lated alcohols. While each of the foregoing and other 29,821-F -2-1 ~55363 conventional demulsifiers are effective in some emul-sions, it is found that many are not as effective as desired, particularly in resolving emulsions derived from steam recovery of heavy crudes by processes typical of some of the California oil fields.
Accordingly, it is highly desirable to pro-vide a demulsification process for resolving emulsions of such heavy crudes as well as other water-in-oil emulsions and the like.
The present invention is such a demulsifi-cation method which comprises contacting an emulsion of oil and water with a demulsifying amount of a quater-nized polyalkylene polyamine which is an adduct of a halohydroxyalkyl quaternary ammonium compound and a lS polyalkylene polyamine.
While the demulsification method of the present invention is particularly effective in resolv-ing emulsions of water in heavy crudes as are commonly recovered from the California oil fields, such demulsi-fication method is also effective for resolving otheremulsions of oil-in-water and water-in-oil.
Emulsions of oil-in-water that are most effectively resolved by the method of this invention are oil field emulsions containing relatively small proportions of crude petroleum oil dispersed in water or brine and are hereinafter characterized as oil-in-water emulsions. Other such oil-in-water emulsions include emulsions in which traces of lubricating oil are found dispersed in steam from steam engines and 29,821-F -3-steam pumps often called steam-cylinder emulsions;
emulsions encountered in the waxing operations in oil refining, often called wax-hexane-water emulsions;
emulsions of flux oil in steam condensate produced in the catalytic dehydrogenation of butylene to produce butadiene; styrene-in-water emulsions and emulsions generated by sewage disposal operations. Although not as preferably resolved as the oil-in-water emulsions, water-in-oil emulsions are suitably treated by the method of this invention. Such water-in-oil emulsions are generally those naturally occurring emulsions of water and petroleum oil wherein the continuous oil phase has tiny droplets of water dispersed therein.
The preferred oil-in-water emulsions may contain widely different proportions of dispersed phase, for example, the oii field emulsions may carry crude oil in proportions varying from a few parts per million to 40 weight percent or higher in rare cases.
All of such emulsions are suitably treated in the practice of this invention, most preferably, however, such oil-in-water emulsions contain from 0.01 to 30 weight percent of oil based on the weight of the emul-sions. Also, while the method of the present invention is effective in treating emulsions derived from light crudes, the method is most effective in treating emul-sions of somewhat heavier crudes wherein the crude has a specific gravity in the range from 0.8 to 0.97 gram/milliliter.
The quaternized polyalkylene polyamines employed in the present invention are adducts of poly-alkylene polyamines and a halohydroxyalkyl quaternary 29,821-F -4-ammonium compound. Exemplary polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylene-tetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, 1-aminoethylpiperazyl diethylene-triamine, 1-aminoethylpiperazyl triethylenetetramine, propylenediamine, dipropylenetriamine, butylenediamine, aminoethylpropylenediamine and other polyamines having at least one primary amino group separated from another primary amino or secondary amino group by 2 to 4 carbon atoms. Of these polyalkylene polyamines, the higher molecular weight polyethylene polyamines and polypropy-lene amines such as those having a number average of 100 to 15,000 are preferred. Of particular interest are the polyalkylene polyamines that are cross-linked with ethylene dichloride as well as mixtures of such cross-linked polyamines with other polyalkylene poly-amines as mentioned hereinbefore.
Reacted with this polyalkylene polyamine is a halohydroxyalkyl quaternary ammonium salt. Examples of such quaternary ammonium salts include 2-hydroxy-3-chloropropyl trimethylammonium chloride, and similar hydroxyhaloalkyl trialkyl ammonium and other halo-hydroxyalkyltrialkyl ammonium halides with 2-hydroxy--3-chloropropyltrimethylammonium chloride being pre-ferred. The adduct of the polyalkylene polyamine andquaternary ammonium salt is advantageously prepared by adding the ~uaternary ammonium salt to the polyalkylene polyamine at ambient temperature. The mixture is then adjusted to alkaline conditions, e.g., pH = 8, by the addition of an aqueous solution of sodium hydroxide or other strong base. The resulting mixture is then heated, e.g., to 90C for 8 hours, until the reaction is completed. While the ratio of the quaternary salt 29,821-F -5-to polyalkylene polyamine in the adduct is not particu-larly critical, it is generally desirable that the molar ratio of quaternary ammonium moiety to amino moiety in the polyalkylene polyamine be in the range from 0.01:1 to 0.8:1, preferably from 0.05:1 to 0.8:1.
In the practice of this invention, the emul-sion to be resolved is contacted with an amount of the adduct which is effective to cause the emulsion to separate into two essentially distinct phases upon standing. Generally, such an amount will be in the range from 1 to 1,000 weight parts of the adduct per million weight parts (ppm) of the emulsion, preferably from 10 to 100 ppm.
The following examples are given to further illustrate the detailed practice of the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
ExamPle 1 To 100 grams of an oil-in-water emulsion containing 10 weight percent of crude oil having a specific gravity of 0.8 g/ml was added 2.4 parts per million based on the emulsion of the reaction product of 1 equivalent of N-~3-chloro-2-hydroxypropyl)-trimethyl ammonium chloride and 1 equivalent of poly-ethylene polyamine having a number average molecular weight of 324. The emulsion was then shaken for 5 minutes to effectively disperse the adduct into the emulsion. Thereafter, the emulsion was allowed to stand for 4 hours after which time the phases separated 29,821-F -6-such that each phase was essentially free of dispersed droplets of the other phase. In a similar manner, different samples of the same emulsion were contacted with different amounts of adducts within the scope of this invention and evaluated for demulsification efficiency. The results of these evaluations are recorded in Table I.
For purposes of comparison, a conventional polyalkylene polyamine demulsifier was similarly added to different samples of the aforementioned emulsion and evaluated for demulsification efficiency. The results of these evaluations are also recorded in Table I.
29,821-F -7-TABLE I
Demulsifying Sample Aqent (1) Demulsification No. TYPeAmount, PPm EfficiencY (2) Cl* Polyamine2.4 3 C2* Polyamine12.2 3 C3* Polyamine24.5 3 l 10% Quat 2.4 4
2 10% Quat12.2 2
3 10% Quat24.5 3
4 25% Quat 2.4 2S% Quat12.2 6 25% Quat24.5 3 7 50% Quat 2.4 8 50% Quat12.2 2 9 50% Quat24.5 3 75% Quat 2.4 11 75% Quat12.2 2 12 75% Quat24.5 3 * Not an example of this invention.
29,821-F -8-g TABLE I (cont'd) (1) Polyamine - polyethylene polyamine having Mn = 50,000 10% Quat - the above polyamine wherein 10 mole percent of the secondary amino groups of the polyamine is quaternized with N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride 2S% Quat - the above polyamine wherein the named mole percent of secondary amino groups is quaternized 50% Quat - the above polyamine wherein the named mole percent of secondary amino groups is quaternized 75% Quat - the above secondary polyamine wherein the named mole percent of amino groups is quaternized (2) Ratings of efficiency are the following:
1 - clear agueous phase, clean interface, good oil 2 - slightly cloudy aqueous phase, clean interface, good oil 3 - cloudy aqueous phase, clean interface, good oil 2S 4 - slight activity, poor interface, some oil breakout As evidenced by the data in Table I, the quaternized polyalkylene polyamines employed in the practice of the present invention, particularly those containing more than 10 mole percent quaternized moiety, are very effective demulsifiers at low concentrations.
29,821-F -9-
29,821-F -8-g TABLE I (cont'd) (1) Polyamine - polyethylene polyamine having Mn = 50,000 10% Quat - the above polyamine wherein 10 mole percent of the secondary amino groups of the polyamine is quaternized with N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride 2S% Quat - the above polyamine wherein the named mole percent of secondary amino groups is quaternized 50% Quat - the above polyamine wherein the named mole percent of secondary amino groups is quaternized 75% Quat - the above secondary polyamine wherein the named mole percent of amino groups is quaternized (2) Ratings of efficiency are the following:
1 - clear agueous phase, clean interface, good oil 2 - slightly cloudy aqueous phase, clean interface, good oil 3 - cloudy aqueous phase, clean interface, good oil 2S 4 - slight activity, poor interface, some oil breakout As evidenced by the data in Table I, the quaternized polyalkylene polyamines employed in the practice of the present invention, particularly those containing more than 10 mole percent quaternized moiety, are very effective demulsifiers at low concentrations.
29,821-F -9-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A demulsification method which comprises contacting an emulsion of oil and water with a demul-sifying amount of a quaternized polyalkylene polyamine which is an adduct of a halohydroxyalkyl quaternary ammonium compound and a polyalkylene polyamine.
2. The method of Claim 1 wherein the emul-sion is an oil-in-water emulsion.
3. The method of Claim 2 wherein the oil phase of the emulsion is crude oil having a density in the range from 0.8 to 0.97 gram/milliliter.
4. The method of Claim 1 wherein the halo-hydroxyalkyl quaternary ammonium compound is a halo-hydroxyalkyl trimethyl ammonium halide.
5. The method of Claim 4 wherein the quaternary ammonium compound is 2-hydroxy-3-chloropropyl trimethyl ammonium chloride.
29,821-F -10-
29,821-F -10-
6. The method of Claim 1 wherein the poly-alkylene polyamine has a number average molecular weight in the range of from 100 to 15,000.
7. The method of Claim 6 wherein the poly-alkylene polyamine is cross-linked with ethylene dichloride.
8. The method of Claim 1 wherein the ratio of quaternary ammonium moiety to amine moiety in the quaternized polyalkylene polyamine is in the range from 0.05:1 to 0.8:1.
9. The method of Claim 1 wherein said demulsifying amount is in the range from 10 to 100 weight parts of quaternized polyalkylene polyamine per million weight parts of the emulsion.
29,821-F -11-
29,821-F -11-
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000391599A CA1155363A (en) | 1981-12-07 | 1981-12-07 | Use of quaternized polyalkylene polyamines as demulsifiers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000391599A CA1155363A (en) | 1981-12-07 | 1981-12-07 | Use of quaternized polyalkylene polyamines as demulsifiers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155363A true CA1155363A (en) | 1983-10-18 |
Family
ID=4121567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391599A Expired CA1155363A (en) | 1981-12-07 | 1981-12-07 | Use of quaternized polyalkylene polyamines as demulsifiers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1155363A (en) |
-
1981
- 1981-12-07 CA CA000391599A patent/CA1155363A/en not_active Expired
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