CA2053227A1 - Process for the separation of oil-in-water emulsions - Google Patents
Process for the separation of oil-in-water emulsionsInfo
- Publication number
- CA2053227A1 CA2053227A1 CA 2053227 CA2053227A CA2053227A1 CA 2053227 A1 CA2053227 A1 CA 2053227A1 CA 2053227 CA2053227 CA 2053227 CA 2053227 A CA2053227 A CA 2053227A CA 2053227 A1 CA2053227 A1 CA 2053227A1
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- Prior art keywords
- oil
- process according
- water
- cationic polymer
- emulsion
- 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.)
- Abandoned
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A B S T R A C T
The present invention relates to a process for the de-mulsification of oil-in-water emulsions by the addi-tion of cationic polymers, which process is character-ized in that a synthetic organic cationic polymer of a) 5 to 70%-wt. of a monomer of the general formula
The present invention relates to a process for the de-mulsification of oil-in-water emulsions by the addi-tion of cationic polymers, which process is character-ized in that a synthetic organic cationic polymer of a) 5 to 70%-wt. of a monomer of the general formula
Description
2 ~ ~
Proces_ for_thQ Se~aration_of 0~ water Emulsions The present invention relates to a process for the separation of oil-water emulsions.
OfW emulsions frequently turn up as contaminated prod-uct streams which, in addition to organic substances, such as mineral oils, vegetable oil, animal oils or fats in emulsified form, also contain non-emulsified substances as well as solid matter.
For exampls~ these mixtures arise in the production of crude oil, when it is transported in oil tankers or pipelines, and during the processing in refineries.
Waste water contaminated with oil and fat also turn up in the metal-working industry, the motorcar industry, in foodstuff manufacturing. workshops and gas sta-tions. Said sewage is heavily loaded and poses great problems for sewage purification plants. It is there-fore absolutely necessary to subject said waste water to special preliminary purification methods before it is introduced into the drainage ditch or the sewage treatment D lant.
Known separation techniques, for example, include flo-tation, filtration, adsorption and sedimentation. In all thesa ~rocesses the organic phase which is present in the water in emulsified form must at first be con-verted into the "free" form. This process is referred to as "cracking of emulsions or demulsification".
The emulsions may be very stable depending on the kind of emulsion and the sort of accompanying substances or ingredients. In order to carry out a physical liquid-2 ~ ~ 3 3 ~ ?~ ~
liquld-phase-separation the emulsion must be cracked in any case. If instable emulsions are concerned, a phase separation may be effected by allowing them to stand for a longer period of time and/or by heating.
To break emulsions stabili~ed with emulsifiers they must be treated with chemical substances to substan-tially discharge the very fine organic, liquid parti-cles which are electrostatically charged in the aque-ous phase. In this case the mutually repelling forces between the organic particles emulsified in water are neutrali~ed, and an agglomeration of the fine droplets takes place which finally results in demulsification by an enlar-gement of the drops.
In general, oil particles in an aqueous emulsion are negatively charged. To reach the isoelectric point cations are added to the emulsion. In addition to the inorganic salts. such as iron (III)- or aluminum salts, and acids, organic water-soluble cationic poly-mers of different chain lengths or molecular weights, respectively, are also used for the same purpose as demulsifiers.
For the purification of oil-containing sewage both cationic and anionic water-soluble Dolymers are fre-quently used irl combination with iron- or aluminum salts. Corresponding purification processes are gen-erally carried out in practice in i-lotations plants af various types, e.g., flash flotation, rnechallical flo-tation, etc.
~ process for the separation of oil from stable O/W-emulsions is described by DE-O~ 19 26 623. The emul-sion is mixed with an iron salt and caustic soda lye and subseque--,tly subjected to a secondary treatment 2~2~
with a high-molecular, water-soluble polymer on the basis of polyacrylic acid, polyacrylamide, polyvinyl alcohol, and polyethylene oxide.
DE-OS 28 41 122 describes the application of cationic, anionic, or non-ionogenic polymers alone or in combi-nation with metal salts for the purification of waste water. Polyamides, polyamines, and copolymers of ac-rylamide with quaternary ammonium polyacrylamides are mentioned as cationic polymer types.
A process employing cationic polymers for the oil-wa-ter-separation is described by U.S. Patent No. 3,691, 086. The polymers are preferably used in combination with silica sol and a multivalent metal salt. Polymers according to this U.S.-Patent 3,691,086 are compared with the polymers according to the present invention in the comparison examples A to F, to demonstrate the qualitatively and quantitatively superior separation achieved by the products according to the present in-vention.
Copolymers of the monomers acrylamide and acryloyl oxiethylenedimethylbenzyl ammonium salts and the use thereof as retention agents in papermaking are de-scribed in ''Chemical Abstracts, vol. 105 (1986) Ref-erence No. 116866c and 116867d.
The processes alld agents for demu`lsi-Fication known from the state cf the art do not achleve a sufficient separation bstween organic phase and water. It is ac-cordingly the object of -the present invention to com-plete the demulsifying action by providing an improved agent for demulsification purposes and to provide a process which leads to a satisfactory separation ~3~2 ~
effect both i!l Tlotation plants and in static separa-tion devices.
In general practice problems with respect to the sepa-ration of oil and water frequently arise when the sep-aration is to take place without a flotation plant by simply allowing the emulsion to stand, e.g., in a tank or a plate separator. These problems frequently arise in offshore crude oil production sites where the pro-vision of a demulsi~ier for O/W emulsions effecting a breaking without energy input into the sewageT like in the rnechanical flotation, and without application of inorganic salts, has been an urgent need.
Most surprisingly it was found that the object accord-ing to the present invention was achieved by the use of a synthetic organic, cationic polymer of a) 5 to 70%-wt. of a monomer of ths general formula IE>
CH2 = C - COY - R2 - N - R4 X (I) I
Rs wherein R1 is -H or -CH3.
Y is -O- or -NH-.
R2 is a straight--chain or branched alkylene greup with ~ to 6 C-atorns, R3, Ra are -CH3 or -CH2 -CH3, Rs is an alkylene-aromatic residue, X is Cl-,CH3 S04 -, 2 ~ r~
b) 20 ~o 95~, acrylamide, and c) 0 to 10% of another water-soluble monomer, e.g., methacrylamide, (meth)acrylic acid, vinyl pyrrolidone, dimethyldiallyl ammonium chloride, acrylamidomethyl propane sulfonic acid, N,N-di-methylacrylamide, vinyl actetamide, or vinyl formamide.
The addition of a cationic polymer of the afore-men-tioned composition in an amount of 0.1 to 50~-wt., preferably 1 to 20%-wt., relative to the organic por-tion of ~he oil-water emulsion, results in demulsifi-cation of this 0/W emulsion. The cationic polymer may be added to the OJW emulsion to be cracked in the form of an emulsion, a powder or of an aqueous so~lution.
The thir~ water-soluble monomer component c) may pre-ferably be acrylic acid or N-vinyl pyrrolidone.
Basic monomers a), which may be quaternized with the residue Rs according to the above definition, particu-larly include:
dimethylaminoethyl acrylate, dimethylaminoethyl meth-acrylate, dimethylaminopropyl acrylamide, dimethyl-aminoprcDyl methacrylamide, diethylam-inoethyl acry-late, dimethylamino-2,2-dimethylpropyl acrylamide.
With respect to the present inventiotl it was most sur-prisingly found that the demulsifying action oF these cationic "poly-quat-types" e~tremely depended on the quaternizing component, i.e., on the kind of the sub-stituent Rs of the general Formula I.
The advantageous results according to the present in-vention are achieved, if as Rs an alkylene-aromatics-
Proces_ for_thQ Se~aration_of 0~ water Emulsions The present invention relates to a process for the separation of oil-water emulsions.
OfW emulsions frequently turn up as contaminated prod-uct streams which, in addition to organic substances, such as mineral oils, vegetable oil, animal oils or fats in emulsified form, also contain non-emulsified substances as well as solid matter.
For exampls~ these mixtures arise in the production of crude oil, when it is transported in oil tankers or pipelines, and during the processing in refineries.
Waste water contaminated with oil and fat also turn up in the metal-working industry, the motorcar industry, in foodstuff manufacturing. workshops and gas sta-tions. Said sewage is heavily loaded and poses great problems for sewage purification plants. It is there-fore absolutely necessary to subject said waste water to special preliminary purification methods before it is introduced into the drainage ditch or the sewage treatment D lant.
Known separation techniques, for example, include flo-tation, filtration, adsorption and sedimentation. In all thesa ~rocesses the organic phase which is present in the water in emulsified form must at first be con-verted into the "free" form. This process is referred to as "cracking of emulsions or demulsification".
The emulsions may be very stable depending on the kind of emulsion and the sort of accompanying substances or ingredients. In order to carry out a physical liquid-2 ~ ~ 3 3 ~ ?~ ~
liquld-phase-separation the emulsion must be cracked in any case. If instable emulsions are concerned, a phase separation may be effected by allowing them to stand for a longer period of time and/or by heating.
To break emulsions stabili~ed with emulsifiers they must be treated with chemical substances to substan-tially discharge the very fine organic, liquid parti-cles which are electrostatically charged in the aque-ous phase. In this case the mutually repelling forces between the organic particles emulsified in water are neutrali~ed, and an agglomeration of the fine droplets takes place which finally results in demulsification by an enlar-gement of the drops.
In general, oil particles in an aqueous emulsion are negatively charged. To reach the isoelectric point cations are added to the emulsion. In addition to the inorganic salts. such as iron (III)- or aluminum salts, and acids, organic water-soluble cationic poly-mers of different chain lengths or molecular weights, respectively, are also used for the same purpose as demulsifiers.
For the purification of oil-containing sewage both cationic and anionic water-soluble Dolymers are fre-quently used irl combination with iron- or aluminum salts. Corresponding purification processes are gen-erally carried out in practice in i-lotations plants af various types, e.g., flash flotation, rnechallical flo-tation, etc.
~ process for the separation of oil from stable O/W-emulsions is described by DE-O~ 19 26 623. The emul-sion is mixed with an iron salt and caustic soda lye and subseque--,tly subjected to a secondary treatment 2~2~
with a high-molecular, water-soluble polymer on the basis of polyacrylic acid, polyacrylamide, polyvinyl alcohol, and polyethylene oxide.
DE-OS 28 41 122 describes the application of cationic, anionic, or non-ionogenic polymers alone or in combi-nation with metal salts for the purification of waste water. Polyamides, polyamines, and copolymers of ac-rylamide with quaternary ammonium polyacrylamides are mentioned as cationic polymer types.
A process employing cationic polymers for the oil-wa-ter-separation is described by U.S. Patent No. 3,691, 086. The polymers are preferably used in combination with silica sol and a multivalent metal salt. Polymers according to this U.S.-Patent 3,691,086 are compared with the polymers according to the present invention in the comparison examples A to F, to demonstrate the qualitatively and quantitatively superior separation achieved by the products according to the present in-vention.
Copolymers of the monomers acrylamide and acryloyl oxiethylenedimethylbenzyl ammonium salts and the use thereof as retention agents in papermaking are de-scribed in ''Chemical Abstracts, vol. 105 (1986) Ref-erence No. 116866c and 116867d.
The processes alld agents for demu`lsi-Fication known from the state cf the art do not achleve a sufficient separation bstween organic phase and water. It is ac-cordingly the object of -the present invention to com-plete the demulsifying action by providing an improved agent for demulsification purposes and to provide a process which leads to a satisfactory separation ~3~2 ~
effect both i!l Tlotation plants and in static separa-tion devices.
In general practice problems with respect to the sepa-ration of oil and water frequently arise when the sep-aration is to take place without a flotation plant by simply allowing the emulsion to stand, e.g., in a tank or a plate separator. These problems frequently arise in offshore crude oil production sites where the pro-vision of a demulsi~ier for O/W emulsions effecting a breaking without energy input into the sewageT like in the rnechanical flotation, and without application of inorganic salts, has been an urgent need.
Most surprisingly it was found that the object accord-ing to the present invention was achieved by the use of a synthetic organic, cationic polymer of a) 5 to 70%-wt. of a monomer of ths general formula IE>
CH2 = C - COY - R2 - N - R4 X (I) I
Rs wherein R1 is -H or -CH3.
Y is -O- or -NH-.
R2 is a straight--chain or branched alkylene greup with ~ to 6 C-atorns, R3, Ra are -CH3 or -CH2 -CH3, Rs is an alkylene-aromatic residue, X is Cl-,CH3 S04 -, 2 ~ r~
b) 20 ~o 95~, acrylamide, and c) 0 to 10% of another water-soluble monomer, e.g., methacrylamide, (meth)acrylic acid, vinyl pyrrolidone, dimethyldiallyl ammonium chloride, acrylamidomethyl propane sulfonic acid, N,N-di-methylacrylamide, vinyl actetamide, or vinyl formamide.
The addition of a cationic polymer of the afore-men-tioned composition in an amount of 0.1 to 50~-wt., preferably 1 to 20%-wt., relative to the organic por-tion of ~he oil-water emulsion, results in demulsifi-cation of this 0/W emulsion. The cationic polymer may be added to the OJW emulsion to be cracked in the form of an emulsion, a powder or of an aqueous so~lution.
The thir~ water-soluble monomer component c) may pre-ferably be acrylic acid or N-vinyl pyrrolidone.
Basic monomers a), which may be quaternized with the residue Rs according to the above definition, particu-larly include:
dimethylaminoethyl acrylate, dimethylaminoethyl meth-acrylate, dimethylaminopropyl acrylamide, dimethyl-aminoprcDyl methacrylamide, diethylam-inoethyl acry-late, dimethylamino-2,2-dimethylpropyl acrylamide.
With respect to the present inventiotl it was most sur-prisingly found that the demulsifying action oF these cationic "poly-quat-types" e~tremely depended on the quaternizing component, i.e., on the kind of the sub-stituent Rs of the general Formula I.
The advantageous results according to the present in-vention are achieved, if as Rs an alkylene-aromatics-
3 ~, 2 ~
residue, such as, in particular, the benzyl group, ispresent as subs~ituent at the quaternary nitrogen atom.
To illustrate the invention, different cationic poly-mers were tested as to their demulsifying action. In this connection, the sewage of a petroleum plant was used as model emulsion and treated in two test series, on the one hand, with known products the character-izing structural feature of which is that Rs = CH3 (referred to as 'comparative product") and, on the other hand, with the product according to the present invention having the same basic structure and differ-ing from the comparative product by the fact that the residue Rs of the general formula I is an alkylene-aromatic according to the definition of the main claim. Tests with Rs = benzyl were also carried out as examples. Homopolymers as described by U.S.-Patent 3,691,086 were used as comparison products E and F.
The following products were tested:
omparative product A: copolymer, consisting of 25%-wt. N-(dimethylamino-propyl)acrylamide, quater-nized with m thyl chloride and 75%-wt. acrylamide.
Product A: copolymer, consisting o~
25%-wt. N-(dimethylamino-propyl~acrylamide, quater-nized with benzyl_chlor_de and 75%-wt. acrylamide.
2 2 ~
omparative product B: cGpolymer, consisting of 70%-wt. N-(dimethylamino-pr^opyl~acrylamide, quater-nized with methyl,,chloride and 30%-wt. acrylamide.
Product B: copolymer, consisting of 70%-wt. N-(dimethylamino-ELPvl)acrYlam _ , quater-nized with benzYl chloride and 30%-wt. acrylamide.
omparative product C: copolymer, consisting of 5~-wt. dimethylaminoethYl _crYlate, quaternized with dimethyl sulf_te and 95%-wt.
acrylamide.
Product C: copolymer, consisting oF
5%-wt. dimethylaminoethyl acrYlate, quaternized with _enzY1 chloride and 95%-wt._ acrylamide.
omparative product D: copolymer, consisting of 50%-wt. dimethylamino-2,2-dimethyl~ropyl acrylamlcie,quaternized with dimethyl sulfate and 50%-wt. acryl-amide Product D: copolymer, consisting of 50%-wt. dimethylamino-2,2-dimethylpropyl acrylamide, cluaternized with be,nzyl 2~3322 i chlorlde and 50%-wt. acryl-annide omparative product E: polymer, consisting of 100%-wt. dimethylaminoet~y~l_meth-acrYlate, quaternized with e_hyl ch_oride.
omparative product F: polymer, consisting of 100%-wt. dimethylaminoethYl meth-_crYlate~ quaternized with be_zyl chloride.
After treatment with the demulsifying cationic polymer according to the present invention the residual oil content in the purified water was determined as heavy lipophilic substances according to DIN 38409, part H
13.
_ample 1_(_est serie~,,_st,,,a,tic separation) In a beaker, the sewage was mi~ed with 50 ppm of each of the above-mentioned comparative products and prod-ucts. The demulsifier was added from a 0.1% aqueous solution. The samples were stirred with a finger blade agitator for 60 seconds at 50 rpm. The emulslon was cracked during this period, when it was then allowed to stand for 30 minutes, tne organic phase settled out at the water surface. Deterrnination of the residual oil contents as difficultly volatile lipophillc sub-stances was carried out for the lower aqueous phase.
~ 3 Exa,m~,l,e_?_,~T,~st serie,s ?,_flo,ta,t_on) The sewage was placed in a 2-liter-laboratory flota-tion cell, type KHD. During stirring at 1,500 rpm and simultaneous introduction of air through a double-walled shaft, 5 ppm demulsifier were added from a 0.1%
aqueous solution; subsequent flotation for ~ minutes.
The organic substances discharged with the foam were separated from the flotation cell by means of a strip-per. The purified water was examined as described above according to DIN 38409, part H 18.
The results of the test series according to Examples 1 and 2 are listed in the following Tables 1 and 2.
Table 1_.
Results of test series l (static separation, Example 1 ) Example Demulsifier Contents of diffi-cultly volatile, lipophilic sub-stances in mg/l, according to DIN
38409, part H 18 1 without addition 68 2 Comparative product A 36 3 Product A l3
residue, such as, in particular, the benzyl group, ispresent as subs~ituent at the quaternary nitrogen atom.
To illustrate the invention, different cationic poly-mers were tested as to their demulsifying action. In this connection, the sewage of a petroleum plant was used as model emulsion and treated in two test series, on the one hand, with known products the character-izing structural feature of which is that Rs = CH3 (referred to as 'comparative product") and, on the other hand, with the product according to the present invention having the same basic structure and differ-ing from the comparative product by the fact that the residue Rs of the general formula I is an alkylene-aromatic according to the definition of the main claim. Tests with Rs = benzyl were also carried out as examples. Homopolymers as described by U.S.-Patent 3,691,086 were used as comparison products E and F.
The following products were tested:
omparative product A: copolymer, consisting of 25%-wt. N-(dimethylamino-propyl)acrylamide, quater-nized with m thyl chloride and 75%-wt. acrylamide.
Product A: copolymer, consisting o~
25%-wt. N-(dimethylamino-propyl~acrylamide, quater-nized with benzyl_chlor_de and 75%-wt. acrylamide.
2 2 ~
omparative product B: cGpolymer, consisting of 70%-wt. N-(dimethylamino-pr^opyl~acrylamide, quater-nized with methyl,,chloride and 30%-wt. acrylamide.
Product B: copolymer, consisting of 70%-wt. N-(dimethylamino-ELPvl)acrYlam _ , quater-nized with benzYl chloride and 30%-wt. acrylamide.
omparative product C: copolymer, consisting of 5~-wt. dimethylaminoethYl _crYlate, quaternized with dimethyl sulf_te and 95%-wt.
acrylamide.
Product C: copolymer, consisting oF
5%-wt. dimethylaminoethyl acrYlate, quaternized with _enzY1 chloride and 95%-wt._ acrylamide.
omparative product D: copolymer, consisting of 50%-wt. dimethylamino-2,2-dimethyl~ropyl acrylamlcie,quaternized with dimethyl sulfate and 50%-wt. acryl-amide Product D: copolymer, consisting of 50%-wt. dimethylamino-2,2-dimethylpropyl acrylamide, cluaternized with be,nzyl 2~3322 i chlorlde and 50%-wt. acryl-annide omparative product E: polymer, consisting of 100%-wt. dimethylaminoet~y~l_meth-acrYlate, quaternized with e_hyl ch_oride.
omparative product F: polymer, consisting of 100%-wt. dimethylaminoethYl meth-_crYlate~ quaternized with be_zyl chloride.
After treatment with the demulsifying cationic polymer according to the present invention the residual oil content in the purified water was determined as heavy lipophilic substances according to DIN 38409, part H
13.
_ample 1_(_est serie~,,_st,,,a,tic separation) In a beaker, the sewage was mi~ed with 50 ppm of each of the above-mentioned comparative products and prod-ucts. The demulsifier was added from a 0.1% aqueous solution. The samples were stirred with a finger blade agitator for 60 seconds at 50 rpm. The emulslon was cracked during this period, when it was then allowed to stand for 30 minutes, tne organic phase settled out at the water surface. Deterrnination of the residual oil contents as difficultly volatile lipophillc sub-stances was carried out for the lower aqueous phase.
~ 3 Exa,m~,l,e_?_,~T,~st serie,s ?,_flo,ta,t_on) The sewage was placed in a 2-liter-laboratory flota-tion cell, type KHD. During stirring at 1,500 rpm and simultaneous introduction of air through a double-walled shaft, 5 ppm demulsifier were added from a 0.1%
aqueous solution; subsequent flotation for ~ minutes.
The organic substances discharged with the foam were separated from the flotation cell by means of a strip-per. The purified water was examined as described above according to DIN 38409, part H 18.
The results of the test series according to Examples 1 and 2 are listed in the following Tables 1 and 2.
Table 1_.
Results of test series l (static separation, Example 1 ) Example Demulsifier Contents of diffi-cultly volatile, lipophilic sub-stances in mg/l, according to DIN
38409, part H 18 1 without addition 68 2 Comparative product A 36 3 Product A l3
4 Comparative product B 28 Product B l2 6 Comparative product C 32 7 Product C lO
8 Comparative product D 35 9 Product D 10 Comparative product E 28 11 Comparative procluct F 29 s~
Table ?
Results of test series 2 (Flotation Example 2) Example Demulsifier Contents of diffi-cultly volatile lipophilic sub-stances in mg/l according to DIN
38409 part H 18 1 without addition 42 2 Comparative product A 6 3 Product A
4 Comparative product B 5 Product B 0.8 6 Comparative product C 4 7 Product C 0.5 a Comparative product D 4.5 9 Product D 0.2 Comparative product E 6 11 Comparative product F 7 The results given in Tables 1 and 2 demonstrate that the addition of the cationic polymers used according to the present invention as demulsifiers results in a by far lower content of heavy lipophilic substances in the sewage.
The results obtained in the tests with the comparative products E and F show that quaterrlized homopolymers both with and without benzyl group result in consider-ably worse separation results comparsd to the copoly-mers used according to the present invention.
8 Comparative product D 35 9 Product D 10 Comparative product E 28 11 Comparative procluct F 29 s~
Table ?
Results of test series 2 (Flotation Example 2) Example Demulsifier Contents of diffi-cultly volatile lipophilic sub-stances in mg/l according to DIN
38409 part H 18 1 without addition 42 2 Comparative product A 6 3 Product A
4 Comparative product B 5 Product B 0.8 6 Comparative product C 4 7 Product C 0.5 a Comparative product D 4.5 9 Product D 0.2 Comparative product E 6 11 Comparative product F 7 The results given in Tables 1 and 2 demonstrate that the addition of the cationic polymers used according to the present invention as demulsifiers results in a by far lower content of heavy lipophilic substances in the sewage.
The results obtained in the tests with the comparative products E and F show that quaterrlized homopolymers both with and without benzyl group result in consider-ably worse separation results comparsd to the copoly-mers used according to the present invention.
Claims (9)
1. A process for the demulsification of oil-in-water emulsions by the addition of cationic polymers, where-in a synthetic organic cationic polymer of a) 5 to 70%-wt. of a monomer of the general formula ( I) wherein R1 is -H or -CH3, Y is -O- or -NH-, R2 is a straight-chain or branched alkylene group with 2 to 6 C-atoms, R3, R4 are -CH3 or -CH2 -CH3, Rs is an alkylene-aromatic residue, X is C1-,CH3SO4-, b) 20 to 95% acrylamide, and c) 0 to 10% of another water-soluble monomer is added to the oil-water emulsion to be demulsified.
2. The process according to claim 1 wherein a cationic polymer is used in which the alkylene group R2 of the general formula (I) contains 2 or 3 C-atoms in straight chain.
3. The process according to claim 1 or 2 wherein a cationic polymer of the general formula (I) is used in which R5 means the group CH2C5H5.
4. The process according to claim 1 or 2 wherein the cationic polymer is added to the oil-water emulsion to be demulsified in the form of an emulsion, a powder, or of an aqueous solution.
5. The process according to claim 1 or 2 wherein the cationic polymer is added at a quantity of 0.1 to 50%-wt., relative to the organic portion of the O/W-emul-sion.
6. The process according to claim 5 wherein the cat-ionic polymer is added at a quantity of 1 to 20%-wt., relative to the organic portion of the O/W-emulsion.
7. The process according to claim 1 or 2 employed to separate oil from sewage.
8. The process according to claim 1 or 2 being a stat-ic or a dynamic separation process.
9. The process according to claim 1 or 2 used in com-bination with a flotation step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893912929 DE3912929A1 (en) | 1989-04-20 | 1989-04-20 | AGENT AND METHOD FOR CLEAVING OIL / WATER EMULSIONS |
| DEP3912929.2 | 1989-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2053227A1 true CA2053227A1 (en) | 1990-10-21 |
Family
ID=6379026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2053227 Abandoned CA2053227A1 (en) | 1989-04-20 | 1990-04-12 | Process for the separation of oil-in-water emulsions |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0398022A1 (en) |
| JP (1) | JP2745244B2 (en) |
| CA (1) | CA2053227A1 (en) |
| DE (1) | DE3912929A1 (en) |
| GR (1) | GR910300036T1 (en) |
| WO (1) | WO1990012633A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5330650A (en) * | 1992-10-30 | 1994-07-19 | Nalco Chemical Company | Dispersion polymers for oil field water clarification |
| KR100216494B1 (en) * | 1993-03-01 | 1999-08-16 | 로날드 제이. 알레인, 지이 엠 브랜논, 더블유 이 패리 | Recovery of oil from waste oil fluid |
| FR2707288B1 (en) * | 1993-07-05 | 1995-09-01 | Atochem Elf Sa | Tertiary butylaminoethyl methacrylate chloride, process for its preparation and its applications. |
| KR100855164B1 (en) * | 2000-10-13 | 2008-08-29 | 니혼아루시 가부시키가이샤 | Flocculants for oil-water separation and method for oil-water separation by flocculation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3691086A (en) * | 1970-07-31 | 1972-09-12 | Hercules Inc | Oil-water separations |
| US4179549A (en) * | 1974-11-14 | 1979-12-18 | Petrolite Corporation | Quaternary ammonium adducts of polymerizable tertiary ammonium salts and acrylamide |
| US4160742A (en) * | 1978-06-15 | 1979-07-10 | Calgon Corporation | Method of resolving oil-in-water emulsions |
| US4454047A (en) * | 1981-03-09 | 1984-06-12 | Petrolite Corporation | Process of treating aqueous systems |
| US4444971A (en) * | 1983-07-25 | 1984-04-24 | Texaco Inc. | Acrylic and methacrylic quaternary chloromethyl ammonium chloride cationic monomers and polymers thereof |
| US4734205A (en) * | 1986-09-08 | 1988-03-29 | Exxon Research And Engineering Company | Hydrophobically associating polymers for oily water clean-up |
-
1989
- 1989-04-20 DE DE19893912929 patent/DE3912929A1/en active Granted
-
1990
- 1990-04-12 EP EP90107042A patent/EP0398022A1/en not_active Withdrawn
- 1990-04-12 CA CA 2053227 patent/CA2053227A1/en not_active Abandoned
- 1990-04-12 EP EP19900905520 patent/EP0468991A1/en active Pending
- 1990-04-12 JP JP2505621A patent/JP2745244B2/en not_active Expired - Lifetime
- 1990-04-12 WO PCT/EP1990/000582 patent/WO1990012633A1/en not_active Application Discontinuation
-
1991
- 1991-11-15 GR GR91300036T patent/GR910300036T1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990012633A1 (en) | 1990-11-01 |
| EP0398022A1 (en) | 1990-11-22 |
| EP0468991A1 (en) | 1992-02-05 |
| DE3912929A1 (en) | 1990-10-31 |
| JPH04504675A (en) | 1992-08-20 |
| DE3912929C2 (en) | 1993-08-26 |
| GR910300036T1 (en) | 1991-11-15 |
| JP2745244B2 (en) | 1998-04-28 |
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| Date | Code | Title | Description |
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| FZDE | Dead |