CN101255354B - Non-polyether type thick oil demulsifying agent and preparation thereof - Google Patents
Non-polyether type thick oil demulsifying agent and preparation thereof Download PDFInfo
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- CN101255354B CN101255354B CN2007100641180A CN200710064118A CN101255354B CN 101255354 B CN101255354 B CN 101255354B CN 2007100641180 A CN2007100641180 A CN 2007100641180A CN 200710064118 A CN200710064118 A CN 200710064118A CN 101255354 B CN101255354 B CN 101255354B
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Abstract
The non-polyether demulsifying agent for thick oil of disclosed by the invention pertains to crude petroleum demulsifying agent for oilfield. The non-polyether demulsifying agent prepared by solution co-polymerization using butyl acrylate and acrylic acid as raw material is proposed to solve the problems of conventional non-polyether demulsifying agent which are complexity in preparation and bad demulsifying effect. The invention adopts method of solution polymerization, improves monomer charging method by charging butyl acrylate in one time, and charging active monomer acroleic acid batchwisely or continuously in copolymerizing process. The copolymer has good amphipathic property, good demulsifying effect, and is suitable for thich oil.
Description
Technical field
The present invention relates to is a kind of crude oil emulsion splitter and preparation method thereof, more particularly, the present invention relates to a kind of non-polyether type oil-field thick-oil emulsion splitter and preparation method thereof.
Background technology
The extraction liquid of viscous crude and other crude oil extraction liquid as many are W/O milk sap, and its water content is 30%～50%.Because viscous crude contains water-oil interface active substances such as higher colloid, bituminous matter, causes the viscosity of viscous crude extraction liquid big, rheological is poor, and interfacial film intensity increases, and drop is the micro emulsion state, stably is dispersed in the external phase.On the other hand at secondary oil recovery later stage and tertiary phase, implement multiple well stimulation such as acidifying, pressure break, water blockoff, profile control and injected various chemical agents (comprising the poly-employed polymkeric substance of technology of adopting), make extraction liquid become and become increasingly complex that crude oil extraction liquid also tends towards stability more.Therefore, need active higher emulsion splitter to finish the viscous crude creaming of emulsion.
Water-soluble and oil-soluble polyethers emulsion splitter is used in China oil field mostly at present.But along with the develop rapidly of petroleum industry and the exploitation of viscous crude, some emulsion splitter shows unable to do what one wishes.Problem in the face of viscous crude emulsion breaking difficulty, each elephant is on the one hand on the basis of original polyether type demulsifying agent, using catalyzer, initiator, chainextender to do some changes and increases relative molecular mass, quicken and improve its demulsification, perhaps carry out the composite composite demulsifying agent that obtains with the single agent of several differences, on the other hand, need be according to the characteristic of viscous crude emulsion, the development of new emulsion splitter.From the trend of the research and development of home and abroad crude oil demulsifier, non-polyethers emulsion splitter also is development in nearly ten a years class emulsion splitter faster.Learn that from some patents the alkylacrylate polymkeric substance can be used for breakdown of emulsion, wherein, U.S. Pat 6080794, US5472617 and US5100582 etc. have and relate to.In addition, Chinese patent CN98113741.5 also is this class in polymer type crude oil demulsifier.The polymerization single polymerization monomer overwhelming majority of these high molecular weight demulsifiers is unsaturated acid and ester class thereof, as the two strong polymerisable monomers of carbon containing carbon such as vinylformic acid, acrylate, alkyl acrylic, alkyl acrylate, toxilic acid, maleic acid ester, vinylbenzene.
Patent US 6080794, US 5472617 and CN98113741.5 also use alkyl acrylate and (methyl) vinylformic acid to carry out copolymerization as raw material, but above-mentioned polymkeric substance several acrylate and the acrylic acid copolymers of adopting more, component is more, complicated process of preparation or to the thick oil emulsion breaking poor effect.
Summary of the invention
The present invention proposes a kind of simple preparation method and non-polyether type thick oil demulsifying agent prepared therefrom for the complicated process of preparation that solves existing non-polyether type demulsifying agent and exist and the problem of thick oil emulsion breaking poor effect.
Non-polyether type thick oil demulsifying agent of the present invention is to be made by butyl acrylate and acrylic acid copolymer, and number-average molecular weight is 5,000～200,000, and molecular formula is as follows:
Wherein, R
3The expression butyl, the content of butyl acrylate segment in described non-polyether type demulsifying agent is 70 quality %～99 quality %, the content of vinylformic acid segment in described non-polyether type demulsifying agent is 1 quality %～30 quality %.In this application, if do not specialize, per-cent is mass percent.
Preferred described non-polyether type demulsifying agent is made by the solution copolymerization method, wherein Butyl Acrylate Monomer is for once feeding intake, Acrylic Acid Monomer adds 20%～50% of vinylformic acid total amount earlier, more preferably adds 30%～40% earlier, adds the residual acrylic acid monomer in polymerization process continuously or in batches.
The present inventor is in order to obtain good demulsification, studies in great detail at the formation and the preparation method of emulsion splitter.According to breakdown of emulsion mechanism design emulsion splitter structure, make emulsion splitter have good hydrophilic radical of balance and hydrophobic grouping.Existing document uses multiple monomer as hydrophilic or hydrophobic grouping in order to regulate the hydrophilic and oleophilic ability of emulsion splitter, but every kind of monomer has different reactivity ratios, must cause homopolymerization or the unbalanced problem of polymerization when copolymerization.The inventor uses vinylformic acid to be hydrophilic monomer, and butyl acrylate is a hydrophobic monomer, calculates reactivity ratio butyl acrylate r=0.30, vinylformic acid r=2.98.Therefore whole butyl acrylates of disposable adding of initial stage and part acrylic acid when polyreaction drip continuously or add residual acrylic acid in batches, can obtain wetting ability and lipophilicity partition ratio multipolymer uniformly, thereby obtain good demulsification.
Specifically, non-polyether type thick oil demulsifying agent of the present invention can use following preparation method to make:
In reactor, add butyl acrylate and solvent, with nitrogen replacement and keep nitrogen atmosphere, under 30～90 ℃, stir, add polymerization starter, the back that stirs adds 20%～50% vinylformic acid, and residual acrylic acid adds continuously or added once every 0.5～3 hour in batches, continue reaction 2～6 hours after all adding vinylformic acid, add polymerization terminator then, reacted again 0.5～1 hour, obtain described non-polyether type thick oil demulsifying agent; Wherein, in butyl acrylate and acrylic acid total mass, the add-on of butyl acrylate is 70%～99%, and acrylic acid add-on is 1%～30%.
In polyreaction, there is no particular limitation to the kind of polymerization starter and polymerization terminator and add-on, and those skilled in the art can select according to general knowledge.For example, in butyl acrylate and acrylic acid gross weight, the add-on of described polymerization starter is preferably 0.1%～2%, and the add-on of described polymerization terminator is preferably 0.1%～2%.Described polymerization starter is preferably azo-compound initiator or organic peroxy compound initiator, for example Diisopropyl azodicarboxylate.Described polymerization terminator is preferably Resorcinol.
In preparation method of the present invention, employed solvent will be applicable to solution polymerization of the present invention, can select arbitrarily in the scope that does not influence emulsion splitter of the present invention, for example, described solvent is aromatic hydrocarbon, alcohol, ketone or ester organic solvent, for example benzene, dimethylbenzene etc.
Polyreaction of the present invention is preferably carried out under 50～90 ℃.
Preferably, the add-on of polyreaction initial stage Acrylic Acid Monomer is 20%～50% of a vinylformic acid total amount, and the monomeric adding mode of residual acrylic acid can be selected to drip continuously or add in batches, and the number of times of Jia Ruing is 2～6 times in batches, more preferably 3 times.The joining day of Acrylic Acid Monomer can equate at interval, also can not wait, and can select according to the needs of polymerization process.
Since when butyl acrylate and acrylic acid copolymer, their reactivity ratio difference, the reactivity ratio r of butyl acrylate
1=0.30＜1, acrylic acid reactivity ratio r
2=2.98＞1, if take the component heterogeneity of the polymkeric substance that once reinforced mode must obtain.Therefore, the present invention improves the monomer addition mode, promptly adopts Butyl Acrylate Monomer for once feeding intake, and Acrylic Acid Monomer adds 20%～50% of vinylformic acid total amount earlier, drips in polymerization process or adds the residual acrylic acid monomer in batches.Monomer is formed constantly in can the maintenance system, and obtaining acrylate and vinylformic acid is the multipolymer of hydrophobic group and hydrophilic group composition distribution uniform, helps entering the crude oil emulsion interface and carries out breakdown of emulsion.This multipolymer has higher surface activity, and can be adsorbed on well and reach demulsification on the water-oil interface.Through industrial application, emulsion splitter demulsification of the present invention is better than the emulsion splitter that industry is now used, and the preparation technology of emulsion splitter of the present invention is simple, and turndown ratio is big, easy handling, and repeatability is high.
Embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is in no way limited to these embodiment.
Embodiment 1
The four-hole boiling flask that agitator, condensation reflux device are housed is placed in the water-bath, bath temperature is raised to 60 ℃, add 41.4 gram butyl acrylates and 55 gram dimethylbenzene, stir, with nitrogen replacement and the continuous nitrogen that feeds.Add 0.25 gram Diisopropyl azodicarboxylate as initiator, stirring adds 1.1 gram vinylformic acid, begins dropwise addition of acrylic acid after spending 15 minutes, drips 2.2 grams in 4 hours, dropwises the back and continues reaction 4 hours.After this, add 0.3 gram Resorcinol as terminator, isothermal reaction is 0.5 hour again, cooling obtains white solution, according to the mensuration of State Standard of the People's Republic of China GB/T1668-95 softening agent acid number and acidity then, use the determination of acid-basetitration carboxyl-content, record and contain 7.40% acrylic acid units, number-average molecular weight is 6.8 ten thousand, molecular weight distribution M
w/ M
nBe 2.68.
Embodiment 2
The four-hole boiling flask that agitator, condensation reflux device are housed is placed in the water-bath, bath temperature is raised to 60 ℃, add 41.4 gram butyl acrylates and 55 gram dimethylbenzene, stir, with nitrogen replacement and the continuous nitrogen that feeds.Add 0.25 gram Diisopropyl azodicarboxylate as initiator, stirring added 1.1 gram vinylformic acid, added 1.1 gram vinylformic acid every 1.5 hours, and vinylformic acid adds three times altogether, and total amount is 3.3 grams, continues reaction 4 hours down at 60 ℃.After this, add 0.3 gram Resorcinol as terminator, isothermal reaction is 0.5 hour again, cooling obtains white solution, according to the mensuration of State Standard of the People's Republic of China GB/T1668-95 softening agent acid number and acidity then, use the determination of acid-basetitration carboxyl-content, record and contain 7.38% acrylic acid units, number-average molecular weight is 6.9 ten thousand, molecular weight distribution M
w/ M
nBe 2.86.
Embodiment 3
The preparation method is with embodiment 2, and different is, solvent is a butanone, and acrylic acid add-on in batches all is 4.8 grams, and acrylic acid total amount is 14.4 grams.According to the mensuration of State Standard of the People's Republic of China GB/T1668-95 softening agent acid number and acidity, with its product determination of acid-basetitration carboxyl-content, record and contain 25.85% acrylic acid units, number-average molecular weight is 7.2 ten thousand, molecular weight distribution M
w/ M
nBe 2.95.
Embodiment 4
The preparation method is with embodiment 2, and different is, solvent is a butanone, and acrylic acid add-on all is 0.2 gram, and acrylic acid total amount is 0.6 gram.According to the mensuration of State Standard of the People's Republic of China GB/T1668-95 softening agent acid number and acidity, with its product determination of acid-basetitration carboxyl-content, record and contain 1.43% acrylic acid units, number-average molecular weight is 5.6 ten thousand, molecular weight distribution M
w/ M
nBe 2.87.
Embodiment 5
The four-hole boiling flask that agitator, condensation reflux device are housed is placed in the water-bath, with nitrogen replacement and the continuous nitrogen that feeds.Bath temperature is raised to 60 ℃, add 41.4 gram butyl acrylates and 55 gram butanone, stir, add 0.08 gram Diisopropyl azodicarboxylate as initiator, stir, add 2.2 gram vinylformic acid, added 1.1 gram vinylformic acid every 1 hour, vinylformic acid adds five times altogether, and it is 6.6 grams that vinylformic acid adds total amount, continues reaction 4 hours down at 60 ℃.After this, add 0.1 gram Resorcinol as terminator, isothermal reaction is 0.5 hour again, cooling obtains white solution, according to the mensuration of State Standard of the People's Republic of China GB/T1668-95 softening agent acid number and acidity then, use the determination of acid-basetitration carboxyl-content, record and contain 13.75% acrylic acid units, number-average molecular weight is 15.6 ten thousand, molecular weight distribution M
w/ M
n=2.56.
Embodiment 6
Present embodiment is an Application Example.
Lonely three crude oil of isolated island: contain 27% water;
Lonely eastern tetrad crude oil: contain 37% water;
Emulsion splitter add-on: 100mg/L
The reference medicament: factory is using emulsion splitter---lonely three emulsion splitters, eastern tetrad emulsion splitter.
Breakdown of emulsion experimental technique: press oil and gas industry standard SY/T5281-2000.
Lonely three crude oil of isolated island have high viscosity, highdensity characteristics, and 50 ℃ of viscosity of crude degree are 899mPas, and oil density is 0.9631g/cm
3, belong to viscous crude.Lonely three extraction liquid are the extraction liquid that contains polymkeric substance, and extraction liquid contains amount of polymers at 80～100mg/L.
The lonely three crude oil demulsification dehydrations experiment of table 1
Below to the east of tetrad crude oil be that sample is estimated emulsion splitter effect of the present invention.
The east tetrad is that the profit of Gu Dong oil recovery factory is handled joint station, and its oil density is 0.9500g/cm
3, colloid, wax and asphalt content are higher, belong to viscous crude.
The eastern tetrad crude oil demulsification dehydration experiment of table 2
See that from the result of top two tables thick oil demulsifier of the present invention has good demulsification performance to viscous crude, breaking emulsion and dewatering efficient all is higher than the emulsion splitter of this oil product rig-site utilization, and water-oil interface are clear, and it is limpid to deviate from water colour.
Claims (9)
1. a non-polyether type thick oil demulsifying agent is characterized in that, described non-polyether type demulsifying agent is made by butyl acrylate and acrylic acid copolymer, and number-average molecular weight is 5,000～200,000, and molecular formula is as follows:
Wherein, R
3The expression butyl, the content of butyl acrylate segment in described non-polyether type demulsifying agent is 70 quality %～99 quality %, the content of vinylformic acid segment in described non-polyether type demulsifying agent is 1 quality %～30 quality %.
2. non-polyether type thick oil demulsifying agent as claimed in claim 1, it is characterized in that, described non-polyether type demulsifying agent is made by the solution copolymerization method, wherein Butyl Acrylate Monomer is for once feeding intake, Acrylic Acid Monomer adds 20%～50% of vinylformic acid total amount earlier, adds the residual acrylic acid monomer in polymerization process continuously or in batches.
3. non-polyether type thick oil demulsifying agent as claimed in claim 1, it is characterized in that, described non-polyether type demulsifying agent is made by the solution copolymerization method, wherein Butyl Acrylate Monomer is for once feeding intake, Acrylic Acid Monomer adds 30%～40% of vinylformic acid total amount earlier, adds the residual acrylic acid monomer in polymerization process continuously or in batches.
4. the preparation method of the described non-polyether type thick oil demulsifying agent of claim 1 is characterized in that, described preparation method is as follows:
In reactor, add butyl acrylate and solvent, with nitrogen replacement and keep nitrogen atmosphere, under 30～90 ℃, stir, add polymerization starter, the back that stirs adds 20%～50% vinylformic acid, and residual acrylic acid adds continuously or added once every 0.5～3 hour in batches, continue reaction 2～6 hours after all adding vinylformic acid, add polymerization terminator then, reacted again 0.5～1 hour, obtain described non-polyether type thick oil demulsifying agent; Wherein, in butyl acrylate and acrylic acid total mass, the add-on of butyl acrylate is 70 quality %～99 quality %, and acrylic acid add-on is 1 quality %～30 quality %.
5. preparation method as claimed in claim 4 is characterized in that, in butyl acrylate and acrylic acid total mass, the add-on of described polymerization starter is 0.1 quality %～2 quality %, and the add-on of described polymerization terminator is 0.1 quality %～2 quality %.
6. preparation method as claimed in claim 4 is characterized in that, described solvent is aromatic hydrocarbon, alcohol, ketone or ester organic solvent, and described polymerization starter is azo-compound initiator or organic peroxy compound initiator, and described polymerization terminator is a Resorcinol.
7. preparation method as claimed in claim 4 is characterized in that described polyreaction is carried out under 50～90 ℃.
8. preparation method as claimed in claim 4 is characterized in that, the monomeric indegree that adds of described residual acrylic acid is 2～6 times.
9. preparation method as claimed in claim 8 is characterized in that, the monomeric indegree that adds of described residual acrylic acid is divided into 3 times.
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| CN105622833B (en) * | 2014-10-28 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of polymer, preparation method and the usage |
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| CN102399576A (en) * | 2010-09-07 | 2012-04-04 | 中国石油化工股份有限公司 | Novel crude oil demulsifier and preparation method thereof |
| CN105504143B (en) * | 2014-09-26 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of non-polyether type demulsifying agent and preparation method thereof |
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| CN113999663A (en) * | 2021-10-11 | 2022-02-01 | 天津大港油田滨港集团博弘石油化工有限公司 | Thick oil viscosity reducer and preparation method thereof |
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