CN1059669A - The preparation method of antiphase emulsion breaker of cation polyether model - Google Patents
The preparation method of antiphase emulsion breaker of cation polyether model Download PDFInfo
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- CN1059669A CN1059669A CN91105181.3A CN91105181A CN1059669A CN 1059669 A CN1059669 A CN 1059669A CN 91105181 A CN91105181 A CN 91105181A CN 1059669 A CN1059669 A CN 1059669A
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Abstract
Antiphase emulsion breaker of cation polyether model preparation method of the present invention is to use initiator and epoxy chloropropane under the acid catalyst effect, is polymerized to the chloro polyethers of molecular weight 1000-2000; Use low-molecular-weight monoamine and chloro polyether reactant again, cationization is cationic polyethers; Prepared cation polyether is as reverse-phase emulsifier, is used for oily(waste)water oil removing and high water-content crude oil and gives and take off free-water, adds several ppm, and oil content of wastewater can be from reducing to below the 20mg/l more than the 10000mg/l.
Description
The invention belongs to the technology of preparing of the cationic demulsifier of water external emulsion.
Contain water-in-oil (W/O) and the dissimilar milk sap of oil-in-water (O/W) in the oil field mining liquid, cause oil, water sepn difficulty.Adopt technique processes such as steam flooding, surfactant flooding, polymer flooding and the alkali displacement of reservoir oil, O/W emulsification degree is serious further; The oil field enters high water-cut development period, and recovered water rolls up, and O/W milk sap is more general.Therefore, along with oil-field development, the de-oiling problem of the breakdown of emulsion of O/W milk sap, oily(waste)water becomes increasingly conspicuous in the oil field mining liquid.The crude oil demulsifier of Cai Yonging all was the emulsion splitter of W/O milk sap in the past, O/W milk sap is not had demulsification, or usefulness was very low.This quasi-oil emulsion splitter generally is referred to as conventional emulsion splitter.Reverse-phase emulsifier is the emulsion splitter of water external emulsion, and de-emulsification speed is fast, the usefulness height.Domestic in the past do not have a reverse-phase emulsifier, generally adopts the nonionic polyoxyalkylene type crude oil demulsifier of three-stage structure such as SP169 etc., reduces the oleaginousness of deviating from sewage.This quasi-oil emulsion splitter, slow to the de-emulsification speed of O/W milk sap, consumption is big, deoiling effect is poor.External the eighties is developed a series of reverse-phase emulsifiers in succession, is used for breakdown of emulsion, the oily(waste)water oil removing of O/W milk sap, is cation type polymer mostly.As u, s, Pat, No, 4,343,730(1982) the middle acrylamide alkylene quaternary ammonium of introducing and the multipolymer of acrylamide; U, s, Pat, No, 4,614,593(1986) the middle monoene propyl group amine polymer of introducing, u, s, Pat, No, 4,686, the diallyldimethylammonium chloride homopolymer of introducing 066(1987), u, s, Pat, No, 4,341, diallyl amine azetidin ammonium and the acrylamide copolymer introduced 887(1982), u, s, Pat, No, 4,689, three (dithiocarbamic acid) compound of introducing in 177(1987) etc.These cationic polymerss, the preparation method is more numerous and diverse, and cost of material is expensive, and the domestic source of goods lacks.
The industrial chemicals that the objective of the invention is to base on our country and be easy to get adopts easy processing method, prepares efficient, cheap positively charged ion reverse-phase emulsifier.
The present invention adopts the synthetic technology route of cationization polyethers, earlier by the epoxy chloropropane ring-opening polymerization, gets the chloro polyethers; Again with low-molecular-weight monoamine with chloro polyethers cationization, cation polyether.The molecular formula of this cation polyether can be expressed as:
Wherein R is an alkyl; N is the integer greater than 10; X is the integer greater than 2;
A is:
Wherein R ' is an alkyl; R " is H or alkyl.
The chloro polyethers be by initiator, epoxy chloropropane under an acidic catalyst effect, adopt the open loop of epoxy compound polymeric method preparation generally know.The molecular weight 1000～2000 of polymkeric substance is suitable for 1500.Polyvalent alcohol or other contain amine, carboxylic acid, phenol of reactive hydrogen etc., can be used as initiator, and glycerol is more suitable.Adoptable an acidic catalyst has ZnCL
2, FeCL
3, boron trifluoride (BF
3)-ether solutions etc., wherein the ether solution of boron trifluoride is more convenient.The polyreaction formula can be expressed as:
Wherein R, n, x are the same.
The cationization reaction of chloro polyethers and low-molecular-weight monoamine mixes reactant earlier, stirs 3～5 hours at 50～70 ℃, is warming up to 90～120 ℃ of reactions 2～3 hours again, and still is pressed and is not more than 0.2MPa.The cation polyether that generates has good water-solubility, and molecular weight is in 1500～3000 scopes, and more suitable molecular weight is 2000.Adopt Mohr's method to measure chloride ion content, thereby determine the ionization degree.Control ionization degree is suitable for 85～95% 70～100%.The low-molecular-weight monoamine that can be used for this purpose has dimethylamine, diethylamine, Trimethylamine 99 and triethylamine etc.; Wherein dimethylamine is comparatively convenient.As if adopting dialkylamine (as dimethylamine), get the tertiary amine cation polyether, if adopt trialkylamine, then get the quaternary ammonium cation polyethers.The cationization reaction formula can be expressed as:
Wherein R, R ', R ", the implication of n, X and A is the same.
The present invention selects for use epoxy chloropropane, low-molecular-weight monoamine as main raw material, domestic ample supply and prompt delivery, and price comparison is cheap; The synthetic technological condition that adopts is simple and easy to do, and intermediate product does not need to make with extra care, and final product does not need aftertreatment yet, can directly be used as reverse-phase emulsifier.Because polymkeric substance is cationic polyelectrolyte, during electronegative O/W emulsion droplets is had and effect such as electric charge, absorption bridging, flocculation be coalescent.Therefore, rp demulsification speed is fast, consumption is few, the oil removal efficiency height.Gudao oilfield recovered water with oleaginousness 11146mg/l is a sample, carries out the rp demulsification benchmark test with the bottle test method, the results are shown in the following table.Data in the table show, under similarity condition, and the reverse-phase emulsifier A that the present invention makes, oil removal efficiency is the highest; When oil removal efficiency was roughly the same, the consumption of the reverse-phase emulsifier A that the present invention makes was minimum.
Rp demulsification performance bottle test evaluation result
| Reverse-phase emulsifier | Add-on (PPm) | Test temperature (℃) | Settling time (min) | Oleaginousness in the water (mg/l) | Oil removal efficiency (%) |
| Reverse-phase emulsifier A FA-252 B2707-B ES-3154 de-emulsifier SP 169 reverse-phase emulsifier A FA-252 ES-3154 de-emulsifier SPs 169 | 18 18 18 18 18 40 60 60 70 | 27 27 27 27 27 29 29 29 29 | 10 10 10 10 10 10 10 10 10 | 260 340 1056 2436 3120 47 47 100 550 | 98 93 91 78 72 99.5 99.5 99.1 95.0 |
FA-252 is an oily demulsifying compound in company of Japanese eastern nation (TOHO) water; B2707-B is U.S. Ai Kesen (EXXON) company reverse-phase emulsifier; ES-3154 is West Germany's BASF (BASF) company reverse-phase emulsifier; SP169 is homemade non-ionic type crude oil demulsifier.
Example A
Adopting common ring-opening polymerization method, make initiator by glycerol, under the katalysis of boron trifluoride-ether solution, is the chloro polyethers (GEP) of molecular weight 1500 with the epoxy chloropropane ring-opening polymerization.
Take by weighing the dimethylamine agueous solution (amido and chlorine are equivalent) of 32g chloro polyethers (GEP) and 35g 40%, place in the clean reactor.With the still sealing, start and stir, exothermic heat of reaction, temperature rises, and still is pressed also and is raise.Maintain the temperature at 50～70 ℃ earlier and stirred 4 hours, again heat temperature raising to 110 ℃ gradually.Stirred 3 hours.Still is pressed and is no more than 0.2MPa.Material is red-brown by the muddiness homogeneous transparent that becomes.Add water 37.6g dilution, get tertiary amine cation polyether solution, concentration 45%(weight).This solution is reverse-phase emulsifier A.Measure chloride ion content, the ionization degree that calculates polymkeric substance is greater than 90%.
Example B
Take by weighing chloro polyethers same among the 37g example A and the trimethylamine aqueous solution of 71g 33%, place in the clean withstand voltage reactor.With the still sealing, start and stir.Earlier 70 ℃ of reactions 5 hours; Heat temperature raising to 120 ℃ continues reaction 8 hours more then.Still is pressed the highest 1MPa.Product is the quaternary ammonium cation polyether aqueous solution, reverse-phase emulsifier B.Measure chloride ion content, calculate the ionization degree greater than 95%.
Example C
By the reverse-phase emulsifier of the present invention preparation, be used for oily(waste)water de-oiling and high water-content crude oil and give and take off free-water and handle, all obtain good effect.As closing treatment station, oil density (20 ℃) 0.9581g/cm at the lonely tetrad of Shengli Oil Field
3, viscosity (50 ℃) 353 * 10
-6m
2/ s.Advance more than the oil content of wastewater 1500mg/l of sewage works.Original with crude oil demulsifier SP169 de-oiling, add continuously in the oil tank import that removes of sewage works, consumption 12PPm, sewage are through the sedimentation oil removing, and again through filter, oleaginousness still more than 100mg/L, does not reach required standard 30mg/l.Use reverse-phase emulsifier A instead, add-on 3.6PPm, under same processing condition, oil content of wastewater can fall below 20mg/l.
Claims (3)
1, antiphase emulsion breaker of cation polyether model is the emulsion splitter of water external emulsion, and technical characterictic of the present invention is by chloro polyethers and low-molecular-weight monoamine reaction, preparation antiphase emulsion breaker of cation polyether model.
2, claim 1 described antiphase emulsion breaker of cation polyether model is to react the tertiary amine cation polyether that makes by chloro polyethers and dimethylamine, diethylamine.
3, claim 1 described antiphase emulsion breaker of cation polyether model is to react the quaternary ammonium cation polyethers that makes by chloro polyethers and Trimethylamine 99, triethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105181.3A CN1027869C (en) | 1991-07-23 | 1991-07-23 | Preparation method of antiphase emulsion breaker of cation polyether model |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105181.3A CN1027869C (en) | 1991-07-23 | 1991-07-23 | Preparation method of antiphase emulsion breaker of cation polyether model |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059669A true CN1059669A (en) | 1992-03-25 |
| CN1027869C CN1027869C (en) | 1995-03-15 |
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|---|---|---|---|
| CN91105181.3A Expired - Fee Related CN1027869C (en) | 1991-07-23 | 1991-07-23 | Preparation method of antiphase emulsion breaker of cation polyether model |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100584C (en) * | 1998-01-21 | 2003-02-05 | 辽河石油勘探局勘察设计研究院 | Polymer type crude oil demulsifier |
| CN100415855C (en) * | 1994-10-06 | 2008-09-03 | 巴斯福股份公司 | Method for breaking emulsification of crude oil |
| CN101357992B (en) * | 2008-06-20 | 2010-12-08 | 中国海洋石油总公司 | Method for preparing stellate poly quaternary ammonium salt high efficient reverse-phase emulsifier |
| CN102153181A (en) * | 2010-11-25 | 2011-08-17 | 中国海洋石油总公司 | Emulsified oil removing agent for waste drilling fluid and preparation method thereof |
| CN101069826B (en) * | 2007-03-19 | 2012-03-21 | 宁波市江北区众合技术开发有限公司 | Efficient general de-emulsifier |
| CN102869422A (en) * | 2010-04-08 | 2013-01-09 | 威廉马什赖斯大学 | Recovery and separation of crude oil and water from emulsions |
| CN102959052A (en) * | 2010-06-24 | 2013-03-06 | 纳尔科公司 | Method for resolving emulsions in enhanced oil recovery operations |
| CN103708677A (en) * | 2013-12-17 | 2014-04-09 | 湖南省电子废弃物处理中心有限公司 | Spraying paint wastewater treatment technology |
| CN104774646A (en) * | 2015-04-22 | 2015-07-15 | 孙豫庆 | Comb type polyether emulsion breaker taking multi-amino polyether as initiator and preparation method of comb type polyether emulsion breaker |
| CN105384927A (en) * | 2015-10-29 | 2016-03-09 | 克拉玛依新科澳石油天然气技术股份有限公司 | Oil-in-water type emulsion demulsifying agent and preparation method thereof |
| CN105873651A (en) * | 2014-01-09 | 2016-08-17 | 陶氏环球技术有限责任公司 | Composition and method for oilfield water clarification processes |
| CN106866954A (en) * | 2017-04-01 | 2017-06-20 | 大庆市富杰化工有限公司 | A kind of cation polyether reverse-phase emulsifier and preparation method thereof |
| CN108136278A (en) * | 2015-10-12 | 2018-06-08 | 艺康美国股份有限公司 | Decompose the method for emulsion formed during ethylene manufactures |
| CN109734876A (en) * | 2018-12-03 | 2019-05-10 | 中国海洋石油集团有限公司 | A kind of polymer-bearing produced fluid reverse-phase emulsifier and preparation method thereof |
| CN111717960A (en) * | 2019-03-22 | 2020-09-29 | 中国石油天然气股份有限公司 | Oily sewage compound type reverse demulsifier and application thereof |
| CN113429955A (en) * | 2021-06-24 | 2021-09-24 | 中国矿业大学 | Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment |
| CN113444237A (en) * | 2021-05-06 | 2021-09-28 | 中海油(天津)油田化工有限公司 | Quaternized polyether reverse demulsifier and preparation method thereof |
| CN113444238A (en) * | 2021-05-06 | 2021-09-28 | 中海油(天津)油田化工有限公司 | Cation-nonionic reverse demulsifier and preparation method thereof |
-
1991
- 1991-07-23 CN CN91105181.3A patent/CN1027869C/en not_active Expired - Fee Related
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415855C (en) * | 1994-10-06 | 2008-09-03 | 巴斯福股份公司 | Method for breaking emulsification of crude oil |
| CN1100584C (en) * | 1998-01-21 | 2003-02-05 | 辽河石油勘探局勘察设计研究院 | Polymer type crude oil demulsifier |
| CN101069826B (en) * | 2007-03-19 | 2012-03-21 | 宁波市江北区众合技术开发有限公司 | Efficient general de-emulsifier |
| CN101357992B (en) * | 2008-06-20 | 2010-12-08 | 中国海洋石油总公司 | Method for preparing stellate poly quaternary ammonium salt high efficient reverse-phase emulsifier |
| CN102869422A (en) * | 2010-04-08 | 2013-01-09 | 威廉马什赖斯大学 | Recovery and separation of crude oil and water from emulsions |
| CN102869422B (en) * | 2010-04-08 | 2015-08-26 | 威廉马什赖斯大学 | Reclaim from emulsion and be separated the method for crude oil and water |
| CN102959052A (en) * | 2010-06-24 | 2013-03-06 | 纳尔科公司 | Method for resolving emulsions in enhanced oil recovery operations |
| CN102959052B (en) * | 2010-06-24 | 2014-12-24 | 纳尔科公司 | Method for resolving emulsions in enhanced oil recovery operations |
| CN102153181B (en) * | 2010-11-25 | 2012-08-29 | 中国海洋石油总公司 | Emulsified oil removing agent for waste drilling fluid and preparation method thereof |
| CN102153181A (en) * | 2010-11-25 | 2011-08-17 | 中国海洋石油总公司 | Emulsified oil removing agent for waste drilling fluid and preparation method thereof |
| CN103708677A (en) * | 2013-12-17 | 2014-04-09 | 湖南省电子废弃物处理中心有限公司 | Spraying paint wastewater treatment technology |
| CN103708677B (en) * | 2013-12-17 | 2016-05-18 | 湖南省电子废弃物处理中心有限公司 | Painting wastewater treatment process |
| CN105873651A (en) * | 2014-01-09 | 2016-08-17 | 陶氏环球技术有限责任公司 | Composition and method for oilfield water clarification processes |
| CN104774646A (en) * | 2015-04-22 | 2015-07-15 | 孙豫庆 | Comb type polyether emulsion breaker taking multi-amino polyether as initiator and preparation method of comb type polyether emulsion breaker |
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| CN106866954B (en) * | 2017-04-01 | 2019-04-26 | 大庆市富杰化工有限公司 | A kind of cation polyether reverse-phase emulsifier and preparation method thereof |
| CN106866954A (en) * | 2017-04-01 | 2017-06-20 | 大庆市富杰化工有限公司 | A kind of cation polyether reverse-phase emulsifier and preparation method thereof |
| CN109734876A (en) * | 2018-12-03 | 2019-05-10 | 中国海洋石油集团有限公司 | A kind of polymer-bearing produced fluid reverse-phase emulsifier and preparation method thereof |
| CN111717960A (en) * | 2019-03-22 | 2020-09-29 | 中国石油天然气股份有限公司 | Oily sewage compound type reverse demulsifier and application thereof |
| CN111717960B (en) * | 2019-03-22 | 2022-06-03 | 中国石油天然气股份有限公司 | Oily sewage compound type reverse demulsifier and application thereof |
| CN113444237A (en) * | 2021-05-06 | 2021-09-28 | 中海油(天津)油田化工有限公司 | Quaternized polyether reverse demulsifier and preparation method thereof |
| CN113444238A (en) * | 2021-05-06 | 2021-09-28 | 中海油(天津)油田化工有限公司 | Cation-nonionic reverse demulsifier and preparation method thereof |
| CN113429955A (en) * | 2021-06-24 | 2021-09-24 | 中国矿业大学 | Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment |
| CN113429955B (en) * | 2021-06-24 | 2022-03-11 | 中国矿业大学 | Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment |
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| Publication number | Publication date |
|---|---|
| CN1027869C (en) | 1995-03-15 |
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