WO2007039083A1 - A process for breaking emulsions or preventing emulsion formation - Google Patents

A process for breaking emulsions or preventing emulsion formation Download PDF

Info

Publication number
WO2007039083A1
WO2007039083A1 PCT/EP2006/009059 EP2006009059W WO2007039083A1 WO 2007039083 A1 WO2007039083 A1 WO 2007039083A1 EP 2006009059 W EP2006009059 W EP 2006009059W WO 2007039083 A1 WO2007039083 A1 WO 2007039083A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsion
water
oil
anhydride
hyperbranched polyesteramide
Prior art date
Application number
PCT/EP2006/009059
Other languages
French (fr)
Inventor
Peter Ernst Froehling
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Publication of WO2007039083A1 publication Critical patent/WO2007039083A1/en

Links

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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

  • the invention relates to a process for breaking emulsions containing oil and water, and also the prevention of the formation of such emulsions.
  • Emulsions can be disadvantageous in e.g. technical, economical or ecological aspect. They may have a viscosity, which is much higher than those of the component phases, which necessitates an increased energy need in pumping or mixing. Corrosion of transport lines or storage vessels may occur due to the presence of e.g. emulsified salt water. Ecological problems may arise due to the presence of emulsified organic components in waste water.
  • Emulsions contain two phases: a continuous phase and a dispersed phase.
  • One component phase is always water, which may contain other dissolved compounds such as salts, solvents or other water-soluble entities.
  • the other phase is often denoted as "oil", and is immiscible with water. Examples of "oil” in this sense are: natural petroleum, liquid hydrocarbons, chloro- and fluorohydrocarbons, silicones and vegetable or animal oils or fats.
  • oil in this sense are: natural petroleum, liquid hydrocarbons, chloro- and fluorohydrocarbons, silicones and vegetable or animal oils or fats.
  • the relative volume fraction of oil in an emulsion can vary between less than 1 % to over 99 %.
  • Undesirable emulsions can be separated into their component phases by a number of methods.
  • the separation process is generally known as "emulsion breaking".
  • emulsion breaking methods are centrifugation, filtration, heating or cooling. For example, these methods are described in the book “Emulsions, theory and practice” by P. Becher (Oxford University Press, 2001).
  • An especially relevant method to break an emulsion is contacting a polymeric compound, which can cause emulsion breaking with the mixture of water and oil. It is also possible to contact a mixture of water and oil with a demulsifier, which mixture is not an emulsion.
  • demulsifiers Such polymers are known as "demulsifiers".
  • demulsifiers in current industrial use are e.g. block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated alkylphenols, ethoxylated alkylphenol-formaldehyde resins, polyvinylalcohol derivatives and cationic or anionic polyelectrolytes. Mixtures of different types of polymers are also used.
  • conventional demulsifiers have certain disadvantages. They can be non-biodegradable, which hinders their application e.g. in wastewater treatment or in offshore oilfield applications.
  • the object of the present invention to provide a process for contacting a mixture of water and oil with a demulsifier, to break the emulsion or to prevent the formation of the emulsion, which process does not possess the above-named disadvantages.
  • the object has been accomplished according to the present invention with a process of contacting a hyperbranched polyesteramide, which is a polycondensate of a di-or trialkanolamine and a cyclic anhydride, with a mixture of water and oil.
  • the mixture may comprise an emulsion of water and oil, and the emulsion is broken into water and oil phases when the emulsion contacts with the hyperbranched polyesteramide.
  • the hyperbranched polyesteramide may be added to the emulsion of water and oil.
  • the hyperbranched polyesteramide may be added to the water or the oil phase, before the water and the oil phase are mixed.
  • the hyperbranched polyesteramide is a polycondensate of a di-or trialkanolamine and a cyclic anhydride.
  • the cyclic anhydride may be preferably selected from the group consisting of succinic anhydride, Ci-Ci 8 alkylsuccinic anhydrides, Ci-Ci 8 alkenylsuccinic anhydrides, polyisobutenylsuccinic anhydride, phthalic anhydride, cyclohexyl-1 ,2- dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride or a mixture of two or more thereof.
  • alkanolamines are di-or trialkanolamines for example diethanolamine, di-isopropanolamine, 2-amino-2-ethyl-1 ,3-propanediol, tris(hydroxymethyl)aminomethane.
  • the emulsion may be an oil-in-water emulsion or a water-in-oil emulsion.
  • the hyperbranched polyesteramide may be preferably a water-soluble hyperbranched polyesteramide.
  • the hyperbranched polyesteramide may be preferably a water soluble hyperbranched polyesteramide prepared by polycondensating a di-or trialkanolamine and a cyclic anhydride selected from the group consisting of succinic anhydride, Ci-Ci 8 alkylsuccinic anhydrides, CrCi 8 alkenylsuccinic anhydrides, and a mixture of two or more thereof.
  • the hyperbranched polyesteramide may be preferably an oil soluble hyperbranched polyesteramide.
  • the hyperbranched polyesteramide may be preferably an oil soluble hyperbranched polyesteramide prepared by polycondensating a di-or trialkanolamine and a cyclic anhydride selected from the group consisting of phthalic anhydride, cyclohexyl-1 , 2-dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride, polyisobutenylsuccinic anhydride or a mixture of two or more thereof.
  • a soluble hyperbranched polyesteramide prepared by polycondensating a di-or trialkanolamine and a cyclic anhydride selected from the group consisting of phthalic anhydride, cyclohexyl-1 , 2-dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride, polyisobutenylsuccinic anhydride or a mixture of two or more thereof.
  • the hyperbranched polyesteramide is added to the mixture of water and oil in a concentration from 1 ppm to 10,000 ppm, more preferably in a concentration from 1 ppm to 1 ,000 ppm, and most preferably in a concentration from 1 to 500 ppm.
  • Hyperbranched polymers are polymers, which contain a large number of branching sites. Contrary to conventional linear polymers which only contain two end groups, hyperbranched polymers possess a large number of end groups, for example on average at least 5 end groups, preferably on average at least ⁇ end groups.
  • the hyperbranched polyesteramides according to the present invention are described in European Patent Publication Nos. EP1036106 and EP1306401 , and International Patent Publication Nos. WO 00/58388 and WO 00/56804.
  • the production of the hyperbranched polyesteramides according to the present invention can be done by polycondensation of alkanolamines and cyclic anhydrides with optional modification of the end groups, as described in above cited patents
  • the chemistry of the polyesteramides allows the introduction of a variety of functionalities, which make these polymers useful as demulsifiers.
  • Preferred functional end groups are -OH, -COOH, -NR 1 R 2 , where R 1 and R 2 can be equal or different alkyl groups from C 1 to C 22 , -OOC-R or -COOR, where R is an alkyl or aralkyl group.
  • Other possible end groups are derived from polymers, e.g. polyethylene glycol, polypropylene glycol, silicones or fluoropolymers.
  • Still other end groups are derived from cyclic compounds, e.g. morpholine, piperidine or derivatives of piperazine.
  • Especially preferred are -OH, alkyl, and polyethylene glycol end groups.
  • the above cited patent publications describe several methods to produce hyperbranched polyesteramides with these functionalities.
  • cyclic anhydride which is used to build up the polymer structure.
  • Preferred cyclic anhydrides with different functionalities are succinic anhydride, alkylsuccinic anhydrides (where the length of the alkyl chain can vary from C 1 to C 18 ), alkenylsuccinic anhydrides (where the length of the alkenyl chain can vary from C 1 to C 18 ), polyisobutenylsuccinic anhydride, phthalic anhydride, cyclohexyl-1 ,2- dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride and other cyclic anhydrides.
  • succinic anhydride and dodecenyl succinic anhydride It is possible to combine more than one type of anhydride to produce a hyperbranched polyesteramide with the desired properties e.g. as a demuls
  • the structure and properties of the polyesteramides according to the present invention can be varied over a broad range of e.g. polarities, solubilities and interfacial activities. This makes the hyperbranched polyesteramides applicable to solve a variety of emulsion problems. Oil-in-water emulsions can be broken by appropriate water-soluble hyperbranched polyesteramides, while water-in-oil emulsions can be broken by appropriate oil-soluble hyperbranched polyesteramides. A man skilled in the art can choose the optimal properties and components needed to provide a demulsifier, which gives the best solution to break an emulsion.
  • the concentration of hyperbranched polyesteramides added to the emulsion mixture may be preferably 1 ppm to 10,000 ppm, more preferably 1 to 1 ,000 ppm, and most preferably 1 to 500 ppm.
  • Another aspect of the present invention is the use of the hyperbranched polyesteramides to prevent emulsion formation. This can be realized by adding the hyperbranched polyesteramide to the water or the oil phase before the water and the oil phase are mixed.
  • a water soluble demulsifier polymer is selected which is to be added to the aqueous phase in order to prevent emulsion formation.
  • an oil soluble demulsifier polymer can be added to the oil phase in order to prevent emulsion formation.
  • the concentration of hyperbranched polyesteramide may vary from 1 ppm to 10,000 ppm, more preferably from 1 to 1,000 ppm, and most preferably from 1 to 500 ppm.
  • the process according to the present invention may for example use one or more hyperbranched polyesteramides in combination or may use formulations comprising other active ingredients as necessitated by specific applications.
  • other ingredients with specific activity are corrosion inhibitors, antifoaming agents, biocides, detergents, rheology modifiers, demulsifiers, flow assurance chemicals and other functions as made necessary by the application.
  • Application of the hyperbranched polyesteramide in the process according to the invention may be as solid or liquid, or dissolved in a solvent which can be chosen by those skilled in the art and as determined by the properties of the specific emulsion.
  • the invention is further illustrated with the following examples.
  • a water soluble hyperbranched polyesteramide was synthesized by the polycondensation at 180 °C of 412 grams of diisopropanolamine, 206 grams of dodecenylsuccinic anhydride and 181 grams of succinic anhydride. The number- average molecular weight of the polymer is about 1500.
  • a stock solution of this hyperbranched polyesteramide 1 was prepared by dissolving 1.4 grams of the polymer in 30.1 grams of water.
  • An emulsion is prepared by mixing 8 grams of n-hexane, 2 grams of water and 0.2 grams of ethoxylated laurylalcohol containing 23 ethylene oxide groups. This resulted in a highly viscous and stable hexane-in-water emulsion.
  • An emulsion is prepared by mixing 20 grams of n-hexane, 20 grams of water and 0.2 grams of ethoxylated laurylalcohol containing 23 ethylene oxide groups as emulsifier. This resulted in a highly viscous and stable hexane-in-water emulsion.
  • the stock solution of Hyperbranched Polyesteramide 1 was further diluted with water to a concentration of 1.82 mg/ml. 25 microliters of this dilute solution were added to 5 ml of Emulsion A (corresponding to about 9 ppm of polymer in the mixture). This resulted in a fast and complete separation of the emulsion into two clear and sharply defined liquid phases.
  • Emulsion B The procedure for preparing Emulsion B was prepared, but 10 microliters of the dilute aqueous solution of Hyperbranched Polyesteramide 1 was added to the water before mixing hexane, water and emulsifier (corresponding to about 1 ppm of polymer in the mixture). When the components were mixed, no emulsion was formed. When the mixing stopped, the components immediately separated into two clear and sharply defined liquid phases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)

Abstract

Process for contacting a mixture of water and oil with a hyperbranched polyester. In the process the formation of an emulsion is prevented. If before the contacting an emulsion was formed, the emulsion is broken. The process is very suitable to be applied during the winning or transportation of crude oil.

Description

A PROCESS FOR BREAKING EMULSIONS OR PREVENTING EMULSION
FORMATION
The invention relates to a process for breaking emulsions containing oil and water, and also the prevention of the formation of such emulsions.
In many types of industrial processes the unintended formation of emulsions presents a major problem. Undesired emulsions may arise in e.g. liquid- liquid extractions, processes for organic synthesis, wastewater treatment, biotechnological fermentations and the production of mineral oil. Emulsions can be disadvantageous in e.g. technical, economical or ecological aspect. They may have a viscosity, which is much higher than those of the component phases, which necessitates an increased energy need in pumping or mixing. Corrosion of transport lines or storage vessels may occur due to the presence of e.g. emulsified salt water. Ecological problems may arise due to the presence of emulsified organic components in waste water. Product losses due to emulsification can be an economic disadvantage. Emulsions contain two phases: a continuous phase and a dispersed phase. One component phase is always water, which may contain other dissolved compounds such as salts, solvents or other water-soluble entities. The other phase is often denoted as "oil", and is immiscible with water. Examples of "oil" in this sense are: natural petroleum, liquid hydrocarbons, chloro- and fluorohydrocarbons, silicones and vegetable or animal oils or fats. When the continuous phase of the emulsion consists of water, the emulsion is known as an oil-in-water emulsion. When the continuous phase consists of oil, the emulsion is called a water-in-oil emulsion. The relative volume fraction of oil in an emulsion can vary between less than 1 % to over 99 %. Undesirable emulsions can be separated into their component phases by a number of methods. The separation process is generally known as "emulsion breaking". Examples of emulsion breaking methods are centrifugation, filtration, heating or cooling. For example, these methods are described in the book "Emulsions, theory and practice" by P. Becher (Oxford University Press, 2001). An especially relevant method to break an emulsion is contacting a polymeric compound, which can cause emulsion breaking with the mixture of water and oil. It is also possible to contact a mixture of water and oil with a demulsifier, which mixture is not an emulsion. In this case the formation of the emulsion is prevented. Such polymers are known as "demulsifiers". Examples of demulsifiers in current industrial use are e.g. block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated alkylphenols, ethoxylated alkylphenol-formaldehyde resins, polyvinylalcohol derivatives and cationic or anionic polyelectrolytes. Mixtures of different types of polymers are also used. However, conventional demulsifiers have certain disadvantages. They can be non-biodegradable, which hinders their application e.g. in wastewater treatment or in offshore oilfield applications. Another disadvantage of certain phenolic demulsifiers is their suspected interference with the human endocrine system. Other demulsifiers are toxic against water organisms. Moreover, there exists no general solution for industrial emulsion problems, and there is a continuous need for new products, which can be active as emulsion breakers.
Accordingly, it is the object of the present invention to provide a process for contacting a mixture of water and oil with a demulsifier, to break the emulsion or to prevent the formation of the emulsion, which process does not possess the above-named disadvantages. The object has been accomplished according to the present invention with a process of contacting a hyperbranched polyesteramide, which is a polycondensate of a di-or trialkanolamine and a cyclic anhydride, with a mixture of water and oil.
Surprisingly it has been found that the process according to the present invention is very effective and can be excecuted with low amounts of non-toxic hyperbranched polyesteramides.
One aspect of the present invention is to provide a process in which hyperbranched polyesteramides are used to break a water/oil emulsion. Another aspect of the present invention is to provide a process in which hyperbranched polyesteramides are used to prevent emulsion formation.
According to a preferable example of the present invention, the mixture may comprise an emulsion of water and oil, and the emulsion is broken into water and oil phases when the emulsion contacts with the hyperbranched polyesteramide. According to a preferable example of the present invention, the hyperbranched polyesteramide may be added to the emulsion of water and oil.
According to another preferable example of the present invention, the hyperbranched polyesteramide may be added to the water or the oil phase, before the water and the oil phase are mixed. The hyperbranched polyesteramide is a polycondensate of a di-or trialkanolamine and a cyclic anhydride.
The cyclic anhydride may be preferably selected from the group consisting of succinic anhydride, Ci-Ci8 alkylsuccinic anhydrides, Ci-Ci8 alkenylsuccinic anhydrides, polyisobutenylsuccinic anhydride, phthalic anhydride, cyclohexyl-1 ,2- dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride or a mixture of two or more thereof.
Examples of alkanolamines are di-or trialkanolamines for example diethanolamine, di-isopropanolamine, 2-amino-2-ethyl-1 ,3-propanediol, tris(hydroxymethyl)aminomethane. According to the preferable example of the invention, the emulsion may be an oil-in-water emulsion or a water-in-oil emulsion.
In case the emulsion is an oil-in-water emulsion, the hyperbranched polyesteramide may be preferably a water-soluble hyperbranched polyesteramide.
The hyperbranched polyesteramide may be preferably a water soluble hyperbranched polyesteramide prepared by polycondensating a di-or trialkanolamine and a cyclic anhydride selected from the group consisting of succinic anhydride, Ci-Ci8 alkylsuccinic anhydrides, CrCi8 alkenylsuccinic anhydrides, and a mixture of two or more thereof.
In case the emulsion is a water-in-oil emulsion, the hyperbranched polyesteramide may be preferably an oil soluble hyperbranched polyesteramide.
The hyperbranched polyesteramide may be preferably an oil soluble hyperbranched polyesteramide prepared by polycondensating a di-or trialkanolamine and a cyclic anhydride selected from the group consisting of phthalic anhydride, cyclohexyl-1 , 2-dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride, polyisobutenylsuccinic anhydride or a mixture of two or more thereof.
Preferable the hyperbranched polyesteramide is added to the mixture of water and oil in a concentration from 1 ppm to 10,000 ppm, more preferably in a concentration from 1 ppm to 1 ,000 ppm, and most preferably in a concentration from 1 to 500 ppm. Hyperbranched polymers are polymers, which contain a large number of branching sites. Contrary to conventional linear polymers which only contain two end groups, hyperbranched polymers possess a large number of end groups, for example on average at least 5 end groups, preferably on average at least δ end groups.
The hyperbranched polyesteramides according to the present invention are described in European Patent Publication Nos. EP1036106 and EP1306401 , and International Patent Publication Nos. WO 00/58388 and WO 00/56804. The production of the hyperbranched polyesteramides according to the present invention can be done by polycondensation of alkanolamines and cyclic anhydrides with optional modification of the end groups, as described in above cited patents
The chemistry of the polyesteramides allows the introduction of a variety of functionalities, which make these polymers useful as demulsifiers. Preferred functional end groups are -OH, -COOH, -NR1R2, where R1 and R2 can be equal or different alkyl groups from C1 to C22, -OOC-R or -COOR, where R is an alkyl or aralkyl group. Other possible end groups are derived from polymers, e.g. polyethylene glycol, polypropylene glycol, silicones or fluoropolymers. Still other end groups are derived from cyclic compounds, e.g. morpholine, piperidine or derivatives of piperazine. Especially preferred are -OH, alkyl, and polyethylene glycol end groups. The above cited patent publications describe several methods to produce hyperbranched polyesteramides with these functionalities.
It is possible, and often even desirable, to combine a number of different end group functionalities in a single hyperbranched polyesteramide molecule in order to obtain desirable properties of the polymer i.e., as a demulsifier.
Another possibility to vary the properties of a hyperbranched polyesteramide is by variation of the cyclic anhydride, which is used to build up the polymer structure. Preferred cyclic anhydrides with different functionalities are succinic anhydride, alkylsuccinic anhydrides (where the length of the alkyl chain can vary from C1 to C18), alkenylsuccinic anhydrides (where the length of the alkenyl chain can vary from C1 to C18), polyisobutenylsuccinic anhydride, phthalic anhydride, cyclohexyl-1 ,2- dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride and other cyclic anhydrides. Especially preferred are succinic anhydride and dodecenyl succinic anhydride. It is possible to combine more than one type of anhydride to produce a hyperbranched polyesteramide with the desired properties e.g. as a demulsifier.
The structure and properties of the polyesteramides according to the present invention can be varied over a broad range of e.g. polarities, solubilities and interfacial activities. This makes the hyperbranched polyesteramides applicable to solve a variety of emulsion problems. Oil-in-water emulsions can be broken by appropriate water-soluble hyperbranched polyesteramides, while water-in-oil emulsions can be broken by appropriate oil-soluble hyperbranched polyesteramides. A man skilled in the art can choose the optimal properties and components needed to provide a demulsifier, which gives the best solution to break an emulsion.
The concentration of hyperbranched polyesteramides added to the emulsion mixture may be preferably 1 ppm to 10,000 ppm, more preferably 1 to 1 ,000 ppm, and most preferably 1 to 500 ppm. Another aspect of the present invention is the use of the hyperbranched polyesteramides to prevent emulsion formation. This can be realized by adding the hyperbranched polyesteramide to the water or the oil phase before the water and the oil phase are mixed. In a system which is expected to form an oil-in- water emulsion, a water soluble demulsifier polymer is selected which is to be added to the aqueous phase in order to prevent emulsion formation. In the case of a- water-in-oil emulsion, an oil soluble demulsifier polymer can be added to the oil phase in order to prevent emulsion formation.
In the use of preventing the formation of emulsions, the concentration of hyperbranched polyesteramide may vary from 1 ppm to 10,000 ppm, more preferably from 1 to 1,000 ppm, and most preferably from 1 to 500 ppm.
The process according to the present invention may for example use one or more hyperbranched polyesteramides in combination or may use formulations comprising other active ingredients as necessitated by specific applications. Examples of other ingredients with specific activity are corrosion inhibitors, antifoaming agents, biocides, detergents, rheology modifiers, demulsifiers, flow assurance chemicals and other functions as made necessary by the application. Application of the hyperbranched polyesteramide in the process according to the invention may be as solid or liquid, or dissolved in a solvent which can be chosen by those skilled in the art and as determined by the properties of the specific emulsion. The invention is further illustrated with the following examples.
Preparation of Hyperbranched Polvesteramide 1
A water soluble hyperbranched polyesteramide was synthesized by the polycondensation at 180 °C of 412 grams of diisopropanolamine, 206 grams of dodecenylsuccinic anhydride and 181 grams of succinic anhydride. The number- average molecular weight of the polymer is about 1500. A stock solution of this hyperbranched polyesteramide 1 was prepared by dissolving 1.4 grams of the polymer in 30.1 grams of water.
Preparation of Hyperbranched Polvesteramide 2 An oil soluble hyperbranched polyesteramide was synthesized by the polycondensation at 180 0C of 118 grams of diisopropanolamine, 301 grams of cyclohexane-1 ,2-dicarboxylic anhydride and 436 grams of polyethyleneglycol monomethylether, containing 7 ethylene oxide groups. The number-average molecular weight of the polymer was 6500.
Preparation of Emulsion A
An emulsion is prepared by mixing 8 grams of n-hexane, 2 grams of water and 0.2 grams of ethoxylated laurylalcohol containing 23 ethylene oxide groups. This resulted in a highly viscous and stable hexane-in-water emulsion.
Preparation of Emulsion B
An emulsion is prepared by mixing 20 grams of n-hexane, 20 grams of water and 0.2 grams of ethoxylated laurylalcohol containing 23 ethylene oxide groups as emulsifier. This resulted in a highly viscous and stable hexane-in-water emulsion.
Example 1
The stock solution of Hyperbranched Polyesteramide 1 was further diluted with water to a concentration of 1.82 mg/ml. 25 microliters of this dilute solution were added to 5 ml of Emulsion A (corresponding to about 9 ppm of polymer in the mixture). This resulted in a fast and complete separation of the emulsion into two clear and sharply defined liquid phases.
Example 2
The procedure for preparing Emulsion B was prepared, but 10 microliters of the dilute aqueous solution of Hyperbranched Polyesteramide 1 was added to the water before mixing hexane, water and emulsifier (corresponding to about 1 ppm of polymer in the mixture). When the components were mixed, no emulsion was formed. When the mixing stopped, the components immediately separated into two clear and sharply defined liquid phases.
Example 3
A crude oil of 15 API gravity, containing 57 % by volume emulsified salt water, was treated with a xylene solution of the Hyperbranched Polyesteramide 2, so that the polymer content was 150 ppm. After 5 hours, more than 95 % of the water content had dropped out of the oil.

Claims

1. A process of contacting a hyperbranched polyesteramide, which is a polycondensate of a di- or trialkanolamine and a cyclic anhydride, with a mixture of water and oil.
2. The process according to claim 1 , wherein the mixture comprises an emulsion of water and oil, and the emulsion is broken into water and oil phases when the emulsion contacts with the hyperbranched polyesteramide.
3. The process according to anyone of claims 1-2, wherein the hyperbranched polyesteramide is added to the emulsion of water and oil
4. The process according to anyone of claims 1-2, wherein the hyperbranched polyesteramide is added to the water or the oil phase before the water and the oil phase are mixed.
5. The process according to any one of claims 2-4, wherein the emulsion is an oil-in-water emulsion or a water-in-oil emulsion.
6. The process according to anyone of claims 2-5, wherein the emulsion is an oil- in-water emulsion and the hyperbranched polyesteramide is a water-soluble hyperbranched polyesteramide.
7. The process according to anyone of claims 2-5, wherein the emulsion is a water-in-oil emulsion and the hyperbranched polyesteramide is an oil soluble hyperbranched polyesteramide
8. The process according to any one of the claims 1-7, wherein the cyclic anhydride is selected from the group consisting of succinic anhydride, C1-Ci8 alkylsuccinic anhydrides, C1-C18 alkenylsuccinic anhydrides, polyisobutenylsuccinic anhydride, phthalic anhydride, cyclohexyl-1 ,2- dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride or a mixture of two or more thereof.
9. The process according to claim 6, wherein the water soluble hyperbranched polyesteramide is prepared by polycondensating a di- or trialkanolamine and a cyclic anhydride selected from the group consisting of succinic anhydride, C1- C18 alkylsuccinic anhydrides, C1-C18 alkenylsuccinic anhydrides, or a mixture of two or more thereof.
10. The process according to claim 7, wherein oil soluble hyperbranched polyesteramide is prepared by polycondensating a di- or trialkanolamine and a cyclic anhydride selected from the group consisting of phthalic anhydride, cyclohexyl-1 ,2-dicarboxylic anhydride, cyclohexen-3,4-yl-1 ,2-dicarboxylic anhydride, polyisobutenylsuccinic anhydride or a mixture of two or more thereof.
11. The process according to any one of the claims 1-10, wherein the hyperbranched polyesteramide is added to the mixture in a concentration from 1 ppm to 10,000 ppm.
12. The process according to claim 11 , wherein the hyperbranched polyesteramide is added to the mixture in a concentration from 1 ppm to 1 ,000 ppm.
PCT/EP2006/009059 2005-09-20 2006-09-18 A process for breaking emulsions or preventing emulsion formation WO2007039083A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05077137 2005-09-20
EP05077137.7 2005-09-20

Publications (1)

Publication Number Publication Date
WO2007039083A1 true WO2007039083A1 (en) 2007-04-12

Family

ID=35520196

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/009059 WO2007039083A1 (en) 2005-09-20 2006-09-18 A process for breaking emulsions or preventing emulsion formation

Country Status (1)

Country Link
WO (1) WO2007039083A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009047210A1 (en) * 2007-10-08 2009-04-16 Basf Se Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions
WO2014158395A1 (en) * 2013-03-14 2014-10-02 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes
JP2015529737A (en) * 2012-09-17 2015-10-08 ディーエスエム アイピー アセッツ ビー．ブイ． Hair care polymer
US9334460B2 (en) 2013-03-14 2016-05-10 Exxonmobil Research And Engineering Company Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US9540576B2 (en) 2013-03-14 2017-01-10 Exxonmobil Research And Engineering Company Hydrohalogenation of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US9617482B2 (en) 2013-03-14 2017-04-11 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes
US9663727B2 (en) 2013-03-14 2017-05-30 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for antifouling in hydrocarbon refining processes
US10597527B2 (en) * 2017-12-21 2020-03-24 Hongbin Zhu Heavy oil demulsifier
CN114106853A (en) * 2021-12-10 2022-03-01 宁波锋成先进能源材料研究院有限公司 Hyperbranched surfactant and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568747A (en) * 1949-06-11 1951-09-25 Visco Products Co Mixed ester amine polybasic acid compositions
US4737550A (en) * 1983-01-07 1988-04-12 The Dow Chemical Company Bridged dense star polymers
EP0267517A2 (en) * 1986-11-13 1988-05-18 Hoechst Aktiengesellschaft Branched polyoxyalkylene polyesters, process for their preparation and their use
EP0325054A2 (en) * 1988-01-21 1989-07-26 Deutsche Ici Gmbh Surfactant composition
DE19651994A1 (en) * 1996-12-13 1998-06-18 Basf Ag Process for the production of self-separating, compact or cellular moldings, optionally containing reinforcing agents, from polyisocyanate polyaddition products and internal mold release agents therefor
WO2003024217A1 (en) * 2001-09-20 2003-03-27 Lonza Inc. Compositions comprising quaternary ammonium compounds and dendritic polymers with antimicrobial activity
EP1306401A1 (en) * 2001-10-29 2003-05-02 Dsm N.V. Oil soluble hyperbranched polyesteramides and method for making the same
DE102005006030A1 (en) * 2005-02-09 2006-08-10 Basf Ag Hyperbranched polymers as demulsifiers for cracking crude oil emulsions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568747A (en) * 1949-06-11 1951-09-25 Visco Products Co Mixed ester amine polybasic acid compositions
US4737550A (en) * 1983-01-07 1988-04-12 The Dow Chemical Company Bridged dense star polymers
EP0267517A2 (en) * 1986-11-13 1988-05-18 Hoechst Aktiengesellschaft Branched polyoxyalkylene polyesters, process for their preparation and their use
EP0325054A2 (en) * 1988-01-21 1989-07-26 Deutsche Ici Gmbh Surfactant composition
DE19651994A1 (en) * 1996-12-13 1998-06-18 Basf Ag Process for the production of self-separating, compact or cellular moldings, optionally containing reinforcing agents, from polyisocyanate polyaddition products and internal mold release agents therefor
WO2003024217A1 (en) * 2001-09-20 2003-03-27 Lonza Inc. Compositions comprising quaternary ammonium compounds and dendritic polymers with antimicrobial activity
EP1306401A1 (en) * 2001-10-29 2003-05-02 Dsm N.V. Oil soluble hyperbranched polyesteramides and method for making the same
DE102005006030A1 (en) * 2005-02-09 2006-08-10 Basf Ag Hyperbranched polymers as demulsifiers for cracking crude oil emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MUSCAT D ET AL: "HYPERBRANCHED POLYESTERAMIDES - NEW DENDRITIC POLYMERS", TOPICS IN CURRENT CHEMISTRY, SPRINGER, BERLIN, DE, vol. 212, 2001, pages 41 - 80, XP001068479, ISSN: 0340-1022 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9296957B2 (en) 2007-10-08 2016-03-29 Basf Se Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions
WO2009047210A1 (en) * 2007-10-08 2009-04-16 Basf Se Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions
US9303215B2 (en) 2007-10-08 2016-04-05 Basf Se Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions
JP2015529737A (en) * 2012-09-17 2015-10-08 ディーエスエム アイピー アセッツ ビー．ブイ． Hair care polymer
US9617482B2 (en) 2013-03-14 2017-04-11 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes
US9085737B2 (en) 2013-03-14 2015-07-21 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes
US9334460B2 (en) 2013-03-14 2016-05-10 Exxonmobil Research And Engineering Company Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US9540576B2 (en) 2013-03-14 2017-01-10 Exxonmobil Research And Engineering Company Hydrohalogenation of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
WO2014158395A1 (en) * 2013-03-14 2014-10-02 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes
US9663727B2 (en) 2013-03-14 2017-05-30 Exxonmobil Research And Engineering Company Functionalized polymers containing polyamine succinimide for antifouling in hydrocarbon refining processes
US9714393B2 (en) 2013-03-14 2017-07-25 Exxonmobil Research And Engineering Company Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US9745528B2 (en) 2013-03-14 2017-08-29 Exxonmobil Research And Engineering Company Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US9777231B2 (en) 2013-03-14 2017-10-03 Exxonmobil Research And Engineering Company Hydrohalogenation of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
US10597527B2 (en) * 2017-12-21 2020-03-24 Hongbin Zhu Heavy oil demulsifier
CN114106853A (en) * 2021-12-10 2022-03-01 宁波锋成先进能源材料研究院有限公司 Hyperbranched surfactant and preparation method thereof
CN114106853B (en) * 2021-12-10 2023-03-07 宁波锋成先进能源材料研究院有限公司 Hyperbranched surfactant and preparation method thereof

Similar Documents

Publication Publication Date Title
WO2007039083A1 (en) A process for breaking emulsions or preventing emulsion formation
Zolfaghari et al. Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum industry
EP2885379B1 (en) Method for resolving emulsions
CA2773803C (en) Dehydrating and desalting median, heavy and extra-heavy oils using ionic liquids and their formulations
CA2773959C (en) Synergistic formulations of functionalized copolymers and ionic liquids for dehydrated and desalted of median, heavy and extra heavy crude oils
RU2577267C2 (en) Raw oil and water extraction and separation from emulsions
Adilbekova et al. Nonionic surfactants based on polyoxyalkylated copolymers used as demulsifying agents
JP2012522634A (en) Demulsified compositions, systems and methods for demulsifying and separating aqueous emulsions
EP2611885A2 (en) Novel copolymers for use as oilfield demulsifiers
CA2280223A1 (en) Method of inhibiting the formation of oil and water emulsions
Xu et al. Breaking water‐in‐bitumen emulsions using polyoxyalkylated DETA demulsifier
Agah et al. Demulsification of saline-in-crude oil via biocompatible cellulose derivative polymers
CN100425317C (en) Demulsifier
US5693216A (en) Method of and composition for breaking oil and water emulsions in crude oil processing operations
Alara et al. Demulsifier: an important agent in breaking crude oil emulsions
Binazadeh Cellulose derivative polymers for demulsification of lagoon wastewater-in-crude oil systems: An efficient water reuse strategy
AU750903B2 (en) Demulsification of oil and water emulsions
CA3062785C (en) Demulsifier or water clarifier activity modifiers
US5730905A (en) Method of resolving oil and water emulsions
Al‐Sabagh et al. Synthesis and evaluation of some polymeric surfactants for treating crude oil—Part II. Destabilization of naturally occurring water‐in‐oil emulsions by polyalkylphenol formaldehyde amine resins
Zaki et al. De-emulsifiers for water-in-crude oil-emulsions: Efficiency of polyalkylphenols-polyalkylenepolyamides-formaldehyde ethoxylates as de-emulsifiers for water-in-crude oil-emulsions
Hamadi Study the effect of glycols base cosolvent additives on breaking of crude oil emulsion
EA026987B1 (en) Cationic vinyl imidazolium-based copolymer for separating an oil-in-water emulsion
Dhandhi et al. Demulsification of Water-in-Crude Oil Field Emulsion Using Green Demulsifier Based on Sesamum indicum: Synthesis, Characterization, Performance, and Mechanism
OA20164A (en) Biodegradable demulsifiers.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06792122

Country of ref document: EP

Kind code of ref document: A1