CN116410453A - Oilfield transition layer treating agent and preparation method and application thereof - Google Patents
Oilfield transition layer treating agent and preparation method and application thereof Download PDFInfo
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- CN116410453A CN116410453A CN202310404689.3A CN202310404689A CN116410453A CN 116410453 A CN116410453 A CN 116410453A CN 202310404689 A CN202310404689 A CN 202310404689A CN 116410453 A CN116410453 A CN 116410453A
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- 230000007704 transition Effects 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000003999 initiator Substances 0.000 claims abstract description 40
- WSNZLQGGHKYFAZ-UHFFFAOYSA-M [Na+].[O-]S(Cl)(=O)=O Chemical compound [Na+].[O-]S(Cl)(=O)=O WSNZLQGGHKYFAZ-UHFFFAOYSA-M 0.000 claims abstract description 30
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 75
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 39
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 38
- 238000011282 treatment Methods 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000008096 xylene Substances 0.000 claims description 25
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- BVIXLMYIFZGRBH-UHFFFAOYSA-M sodium;2-chloroethanesulfonate Chemical group [Na+].[O-]S(=O)(=O)CCCl BVIXLMYIFZGRBH-UHFFFAOYSA-M 0.000 claims description 3
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- 239000003921 oil Substances 0.000 abstract description 27
- 239000010779 crude oil Substances 0.000 abstract description 16
- 238000009296 electrodeionization Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000000368 destabilizing effect Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- QBQVXXQXZXDEHE-UHFFFAOYSA-M sodium;propane-1-sulfonate;hydrate Chemical compound O.[Na+].CCCS([O-])(=O)=O QBQVXXQXZXDEHE-UHFFFAOYSA-M 0.000 description 21
- 230000002829 reductive effect Effects 0.000 description 19
- 239000011206 ternary composite Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- -1 polyoxypropylene Polymers 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- ONGGURNBDHMMTE-UHFFFAOYSA-N ClCC(C[Na])O Chemical compound ClCC(C[Na])O ONGGURNBDHMMTE-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000379 polypropylene carbonate Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to an oilfield transition layer treating agent, a preparation method and application thereof. The method comprises the following steps: carrying out a first polymerization reaction on an initiator with an amino end group and propylene carbonate to obtain a first intermediate; carrying out a second polymerization reaction on the first intermediate and ethylene carbonate to obtain a second intermediate; and (3) reacting the second intermediate with sodium chlorosulfonate to obtain the oilfield transition layer treating agent. The oil field transition layer treating agent prepared by the invention has good inhibiting and destabilizing effects on a transition layer formed in the crude oil electrodeionization process, reduces the running current of an electric dehydrator and the water content of crude oil to a great extent, effectively improves the running voltage of the electric dehydrator, and can effectively reduce the petroleum exploitation cost, save energy and reduce emission.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, and relates to an oilfield transition layer treating agent, a preparation method and application thereof.
Background
With the continuous increase of the concentration of the oil displacement agent in the produced liquid, the difficulty of oil-water separation of the produced liquid is gradually increased. The three-phase composite stable complex transition layer is formed between oil-water interfaces in the oil-water separation process, prevents oil drops from floating up and water drops from sinking down, and has the characteristics of high conductivity and strong stability. Especially when the oil well at the front end of the dehydration station is fractured, the pipeline is cleaned, and the aged oil is recovered, the transition layer in the electric dehydrator can be enriched in a large amount, so that the electric dehydrator is unstable to operate, the phenomenon of blackening water or even crossing an electric field occurs, and the stability of the water content of the outer oil transportation is affected to reach the standard.
At present, in order to ensure the stable operation of an electric dehydrator, the influence of a transition layer on a dehydration system is reduced in an oil field, and mainly two modes are adopted: on one hand, the dosage of the demulsifier at the front section is increased, the oil-water separation effect at the front section is improved, and the oil content in the water discharged at the second section is reduced; on the other hand, the two-stage water discharge amount is increased, and the transition layer is discharged to a settling tank or an accident tank. The existing ternary composite flooding produced liquid has been applied with various demulsifiers, for example, the demulsifiers with larger usage amount are polyoxypropylene polyoxyethylene ether demulsifiers prepared by using ethylene oxide and propylene oxide as raw materials, and the traditional polyether demulsifiers mainly use ethylene oxide and propylene oxide to form block polymers. The existing demulsifier has poor treatment effect on the transition layer, so that the operation of the rear-stage electric dehydrator is unstable, and a cross-electric field phenomenon occurs; the drainage of the transition layer from the interior of the electric dehydrator through the bottom water results in loss of crude oil production. In addition, the transition layer accumulated in the settling tank cannot be effectively treated under the existing aging oil treatment process, so that the transition layer is in vicious circle in the system and affects the downstream water quality.
Although a plurality of different demulsifiers are applied to the treatment of the ternary composite flooding produced liquid in the prior art, the demulsifiers have still not ideal treatment effect on the transition layer in the electric dehydration process, so that a new oil field transition layer treating agent still needs to be continuously researched and explored, and the demulsifiers have very important significance for improving the stable operation of the oil field electric dehydrator, reducing the water content of the oil phase, the operation current of the electric dehydrator and other performance indexes.
Therefore, it is very necessary to provide an oilfield transition layer treatment agent, and a preparation method and application thereof.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides an oilfield transition layer treating agent, and a preparation method and application thereof. The oil field transition layer treating agent prepared by the invention has good inhibiting and destabilizing effects on a transition layer formed in the crude oil electrodeionization process, reduces the running current of an electric dehydrator and the water content of crude oil to a great extent, effectively improves the running voltage of the electric dehydrator, and can effectively reduce the petroleum exploitation cost, save energy and reduce emission.
The invention provides a preparation method of an oilfield transition layer treating agent in a first aspect, which comprises the following steps:
(1) Carrying out a first polymerization reaction on an initiator with an amino end group and propylene carbonate to obtain a first intermediate;
(2) Carrying out a second polymerization reaction on the first intermediate and ethylene carbonate to obtain a second intermediate;
(3) And (3) reacting the second intermediate with sodium chlorosulfonate to obtain the oilfield transition layer treating agent.
Preferably, the molar ratio of the propylene carbonate to the initiator is (6-40): 1, a step of; and/or the molar ratio of the ethylene carbonate to the initiator is (20-80): 1.
preferably, the first polymerization reaction and the second polymerization reaction are carried out under the action of a catalyst A, wherein the catalyst A is one or more of potassium hydroxide, potassium carbonate and triethylamine; preferably, the catalyst A is used in an amount of 0.5 to 3% by mass of the propylene carbonate.
Preferably, the temperature of the first polymerization reaction and/or the second polymerization reaction is 100-130 ℃ and the time is 2-6 h; in step (2), the ethylene carbonate is added in the form of an ethylene carbonate solution; preferably, the ethylene carbonate solution takes xylene and/or chlorobenzene as a solvent; preferably, the ethylene carbonate solution contains 50 to 90 mass percent of ethylene carbonate.
Preferably, in step (3): the reaction is carried out under the action of a catalyst B, wherein the catalyst B is potassium hydroxide and/or sodium hydroxide, and preferably, the dosage of the catalyst B is 2-8% of the mass of the second intermediate; and/or the sodium chlorosulfonate is added in the form of a sodium chlorosulfonate aqueous solution, and preferably, the sodium chlorosulfonate aqueous solution contains 5-15% by mass of sodium chlorosulfonate.
Preferably, in step (3): the sodium chlorosulfonate is sodium 2-chloroethyl sulfonate and/or sodium 3-chloro-2-hydroxy propane sulfonate; the molar ratio of the sodium chlorosulfonate to the second intermediate is (1-3): 1, a step of; in the step (3), the temperature of the reaction is 60-90 ℃, and the time of the reaction is 10-24 hours.
Preferably, the preparation of the initiator comprises the following steps:
(a) Taking short-chain alcohol as a solvent, and enabling fatty amine and methyl acrylate to perform a first reaction to obtain a first reaction product;
(b) And (3) taking short-chain alcohol as a solvent, and carrying out a second reaction on the first reaction product and ethylenediamine to obtain the initiator with the end group of amino.
Preferably, the first reaction and/or the second reaction is: reacting for 12-24 h at room temperature; said methyl acrylate and said fatty amineThe molar ratio is (2-6): 1, a step of; the mol ratio of the ethylenediamine to the fatty amine is (2-6): 1, a step of; in the step (a) and/or the step (b), the dosage of the short-chain alcohol accounts for 60-90% of the total mass of the reaction system; the fatty amine is C in alkyl chain 4 ～C 20 Preferably, the fatty amine is n-dodecyl amine and/or n-octyl amine; and/or in step (a) and step (b), the short-chain alcohol is one or more of methanol, ethanol, n-propanol, isopropanol.
The present invention provides in a second aspect an oilfield transition treatment agent prepared by the method of the invention described in the first aspect.
The invention provides in a third aspect the use of an oilfield transition layer treatment agent prepared by the preparation method of the invention in the first aspect for treating a ternary complex flooding produced fluid transition layer.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The oil field transition layer treating agent prepared by the invention integrates multiple actions of chelation, electric neutralization, displacement, coalescence and the like, has safe preparation process and raw materials, simple and convenient operation steps and low cost, has good treatment effect on the ternary complex flooding complex produced liquid transition layer, and is suitable for industrial popularization and application.
(2) The oil field transition layer treating agent prepared by the invention has good inhibiting and destabilizing effects on a transition layer formed in the crude oil electrodeionization process, reduces the running current of an electric dehydrator and the water content of crude oil to a great extent, effectively improves the running voltage of the electric dehydrator, and can effectively reduce the petroleum exploitation cost, save energy and reduce emission; after the oilfield transition layer treating agent in some preferred embodiments of the invention is electrically removed in an electric dehydrator for treating ternary complex flooding produced liquid, the volume compression rate of the transition layer is as high as more than 50%, the current reduction amplitude is as high as more than 45%, and the water content of an oil phase is reduced by more than 60%.
Drawings
FIG. 1 is a flow chart of preparation in some embodiments of the invention;
FIG. 2 is an infrared spectrum of the initiator in example 1;
FIG. 3 is an infrared spectrum of the second intermediate in example 1;
FIG. 4 is a graph of transition volume versus concentration of oilfield transition treatment agent after electrodeionization in an electrodehydrator added to treat a simulated emulsion using the oilfield transition treatment agent of example 1;
FIG. 5 is a graph of water cut in oil versus field transition layer treatment concentration after electrodeionization in an electrodehydrator added to treat a simulated emulsion using the field transition layer treatment of example 1;
FIG. 6 is a graph of current values versus oilfield transition treatment agent concentration after electrodeionization in an electrodehydrator added to treat a simulated emulsion using the oilfield transition treatment agent of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an oilfield transition layer treating agent in a first aspect, which comprises the following steps:
(1) Carrying out a first polymerization reaction on an initiator with an amino end group and propylene carbonate to obtain a first intermediate; the invention does not require any specific requirement for the amine-terminated initiator, preferably the initiator is a hyperbranched molecule, for example, polyamide-amine with amine-terminated can be used as the initiator;
(2) Carrying out a second polymerization reaction on the first intermediate and ethylene carbonate to obtain a second intermediate (hyperbranched polycarbonate);
(3) And (3) reacting the second intermediate with sodium chlorosulfonate to obtain the oilfield transition layer treating agent (abbreviated as transition layer treating agent).
Firstly, synthesizing hyperbranched molecules of two-block polycarbonate containing lipophilic groups and demulsification groups by taking an initiator, ethylene carbonate, propylene carbonate and the like as main raw materials, and then carrying out intramolecular recombination on the hyperbranched molecules and sodium chlorosulfonate reaction to obtain the oilfield transition layer treating agent; wherein, ethylene carbonate and propylene carbonate are non-dangerous chemicals, and the ring-opening polymerization process is safer; compared with polyoxyethylene ether or polyoxypropylene ether demulsifier using ethylene oxide and propylene oxide as raw materials, the demulsifier has lower cost and higher production and use safety; the oil field transition layer treating agent prepared by the invention integrates multiple actions of chelation, electric neutralization, displacement, coalescence and the like, has good inhibiting and destabilizing effects on the ternary complex flooding complex produced liquid transition layer, reduces the running current of an electric dehydrator and the water content of crude oil to a great extent, effectively improves the running voltage of the electric dehydrator, can effectively reduce the petroleum exploitation cost, saves energy and reduces emission, and is suitable for industrial popularization and application.
According to some preferred embodiments, the molar ratio of propylene carbonate to the initiator is (6-40): 1 (e.g., 6:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, or 40:1); and/or the molar ratio of the ethylene carbonate to the initiator is (20-80): 1 (e.g., 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, or 80:1).
In the present invention, it is preferable that the molar ratio of the propylene carbonate to the initiator is (6 to 40): 1, the molar ratio of the ethylene carbonate to the initiator is (20-80): 1, so that the polyvinyl carbonate block and the polypropylene carbonate block with proper lengths can be obtained through two-step polymerization reaction, the treatment effect of the treatment agent for the transition layer of the oil field is improved, the running current of the electric dehydrator and the water content of crude oil can be reduced to a greater extent, and if the mole ratio of the propylene carbonate to the initiator and the mole ratio of the ethylene carbonate to the initiator are not proper, the displacement effect of the transition layer of the oil field and the like can be influenced, and the treatment effect is influenced.
According to some preferred embodiments, the first polymerization reaction and the second polymerization reaction are carried out under the action of a catalyst a, which is one or more of potassium hydroxide, potassium carbonate, triethylamine; preferably, the catalyst a is used in an amount of 0.5 to 3% (e.g., 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8% or 3%) by mass of the propylene carbonate.
According to some preferred embodiments, the temperature of the first polymerization reaction and/or the second polymerization reaction is 100-130 ℃ (e.g., 100 ℃, 105 ℃, 110 ℃,115 ℃, 120 ℃, 125 ℃, or 130 ℃) for a period of 2-6 hours (e.g., 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 hours); in the step (2), the ethylene carbonate is added in the form of an ethylene carbonate solution, preferably, the ethylene carbonate is added dropwise to the polymerization system in the form of an ethylene carbonate solution at a rate of, for example, 1 to 5 drops/sec; preferably, the ethylene carbonate solution takes xylene and/or chlorobenzene as a solvent; in some specific embodiments, taking the ethylene carbonate solution as an example of a ethylene carbonate xylene solution, that is, a xylene solution in which ethylene carbonate is prepared into ethylene carbonate using xylene, it is preferable that the ethylene carbonate solution contains 50 to 90% by mass (for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%) of ethylene carbonate.
According to some preferred embodiments, in step (3): the reaction is carried out under the action of a catalyst B, which is potassium hydroxide and/or sodium hydroxide, preferably in an amount of 2-8% (e.g. 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%) of the mass of the second intermediate; in the step (3), a mixed solvent containing short-chain alcohol and water is used as a solvent for reaction, wherein the short-chain alcohol is one or more of methanol, ethanol, n-propanol and isopropanol, and the mass ratio of the short-chain alcohol to the water is (1-5): 1 (e.g. 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1), in particular, for example, the reaction is carried out with a short-chain alcohol and water as mixed solvent, the water being brought into the reaction system by means of an aqueous solution of sodium chlorosulfonate, i.e. the mass ratio of the short-chain alcohol to the water contained in the aqueous solution of sodium chlorosulfonate is (1-5): 1, a step of; and/or the sodium chlorosulfonate is added in the form of an aqueous solution of sodium chlorosulfonate, preferably, the aqueous solution of sodium chlorosulfonate contains 5-15% by mass (e.g., 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%).
In the present invention, for the step (3), the reaction is carried out under the action of the catalyst B, with the short-chain alcohol and water as a mixed solvent, specifically, for example, the second intermediate and the catalyst B may be dissolved in the short-chain alcohol, and then an aqueous solution of sodium chlorosulfonate may be added to carry out the reaction.
According to some preferred embodiments, in step (3): the sodium chlorosulfonate is sodium 2-chloroethyl sulfonate and/or sodium 3-chloro-2-hydroxy propane sulfonate; the molar ratio of the sodium chlorosulfonate to the second intermediate is (1-3): 1 (e.g., 1, 1.5:1, 2:1, 2.5:1, or 3:1) is preferably 2:1; in the present invention, the molar ratio of the sodium chlorosulfonate to the second intermediate is preferably (1 to 3): 1, so that the treatment effect of the oilfield transition layer treatment agent is more favorable, the running current of an electric dehydrator and the water content of crude oil can be reduced to a greater extent, the invention discovers that if the dosage of sodium chlorosulfonate is too large, the hydrophilicity of the oilfield transition layer treatment agent product is too strong, the oilfield transition layer treatment agent is easier to enter into an aqueous phase, the micellization effect is enhanced, the treatment effect on the oilfield crude oil transition layer with relatively low water content is reduced, and conversely, if the dosage of sodium chlorosulfonate is too small, for example, when the molar ratio of the sodium chlorosulfonate to the second intermediate is lower than 1:1, the content of formed cationic groups (quaternary ammonium groups) is reduced, the electric neutralization effect of the oilfield transition layer treatment agent is reduced, and the treatment effect is reduced.
According to a preferred embodiment, in step (3), the temperature of the reaction is 60 to 90 ℃ (e.g. 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃), and the time of the reaction is 10 to 24 hours (e.g. 10, 12, 14, 16, 18, 20, 22 or 24 hours).
According to some preferred embodiments, the preparation of the starter comprises the steps of:
(a) Taking short-chain alcohol as a solvent, and enabling fatty amine and methyl acrylate to perform a first reaction to obtain a first reaction product;
(b) And (3) taking short-chain alcohol as a solvent, and carrying out a second reaction on the first reaction product and ethylenediamine to obtain the initiator with the end group of amino.
According to some specific embodiments, the preparation of the starter is: using short-chain alcohol as solvent to make alkyl chain be C 4 ～C 20 The aliphatic amine of (2) reacts with methyl acrylate and ethylenediamine in turn for 12-24 hours at room temperature, and the initiator hyperbranched macromolecule with one end being amino is obtained through reduced pressure distillation.
According to some preferred embodiments, the first reaction and/or the second reaction is: reacting at room temperature (e.g., room temperature 15-35 ℃) for 12-24 hours (e.g., 12, 14, 16, 18, 20, 22, or 24 hours); the molar ratio of the methyl acrylate to the fatty amine is (2-6): 1 (e.g., 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1); the mol ratio of the ethylenediamine to the fatty amine is (2-6): 1 (e.g., 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1); the molar ratio of ethylenediamine to the first reaction product is, for example, (2-8): 1, a step of; in step (a) and/or step (b), the short-chain alcohol is used in an amount of 60 to 90% (e.g., 60%, 65%, 70%, 75%, 80%, 85% or 90%) of the total mass of the reaction systems, in other words, in step (a), the reaction system of the first reaction contains 60 to 90% by mass of the short-chain alcohol, and/or in step (b), the reaction system of the second reaction contains 60 to 90% by mass of the short-chain alcohol; the fatty amine is C in alkyl chain 4 ～C 20 Preferably, the fatty amine is n-dodecyl amine and/or n-octyl amine; and/or in step (a) and step (b), the short-chain alcohol is one or more of methanol, ethanol, n-propanol, isopropanol.
According to some specific embodiments, the preparation of the oilfield transition treatment agent comprises the steps of:
(1) using short-chain alcohol as solvent to make alkyl chain be C 4 ～C 20 The aliphatic amine of (2) is sequentially reacted with methyl acrylate and ethylenediamine at room temperature for 12-24 hours respectively, and then the initiator hyperbranched macromolecule with one end being amino is obtained through reduced pressure distillation; wherein the molar ratio of methyl acrylate to fatty amine is (2-6): 1, the mol ratio of ethylenediamine to fatty amine is (2-6): 1, the dosage of the short-chain alcohol accounts for 60-100% of the total mass of the reaction system;
(2) under the action of a catalyst A, enabling an initiator to react with propylene carbonate and ethylene carbonate at constant temperature of 100-130 ℃ for 2-6 hours respectively to obtain an intermediate of the two-block polycarbonate containing lipophilic groups and demulsification groups; the two-block polycarbonate obtained in the present invention has a first block which is a polypropylene carbonate block and a second block which is a polyethylene carbonate block, and the polypropylene carbonate block and the polyethylene carbonate block have both a segment having no transesterification and a segment having no transesterification, but the reaction temperature is relatively low to produce a polypropylene carbonate block having no transesterification and a polyethylene carbonate block having no transesterification, respectively;
(3) under the action of a catalyst B, short-chain alcohol and water are used as mixed solvents, so that the intermediate obtained in the step (2) reacts with sodium chlorosulfonate for 10-24 hours at 60-90 ℃, and the oil field transition layer treating agent is obtained through alcohol washing and separation.
The present invention provides in a second aspect an oilfield transition treatment agent prepared by the method of the invention described in the first aspect.
The invention provides in a third aspect the use of an oilfield transition layer treatment agent prepared by the preparation method of the invention in the first aspect for treating a ternary complex flooding produced fluid transition layer.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The reaction materials used in the examples of the present invention and comparative examples were all commercially available without particular explanation.
Example 1
(1) Dissolving 0.02mol of n-dodecyl amine in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.08mol of methyl acrylate into the solution, then performing a first reaction at room temperature of 25 ℃ for 24 hours, and removing excessive methyl acrylate and methanol by reduced pressure distillation after the reaction is finished to obtain a first reaction product with an end group being an ester group, wherein in the first reaction, the dosage of the methanol accounts for 60% of the total mass of a first reaction system, and in the first reaction, the speed of dropwise adding the methyl acrylate is 1 drop/second; dissolving 0.01mol of the first reaction product in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.06mol of ethylenediamine into the reaction product, then performing a second reaction at room temperature of 25 ℃ for 24 hours, and removing excessive ethylenediamine and methanol by reduced pressure distillation after the reaction is finished to obtain an initiator with an amino end group, wherein the yield is 95.56%, the dosage of the methanol accounts for 69% of the total mass of a second reaction system in the second reaction, and the speed of dropwise adding the ethylenediamine is 1 drop/second in the second reaction.
(2) Heating 0.01mol of the initiator obtained in the step (1) and potassium hydroxide to 100 ℃ in an inert atmosphere (nitrogen atmosphere), slowly dropwise adding 0.2mol of propylene carbonate, and then carrying out constant temperature reaction for 4 hours at 120 ℃ to obtain a first intermediate; slowly dripping a vinyl carbonate xylene solution into the first intermediate, reacting at a constant temperature of 120 ℃ for 4 hours, and cooling to room temperature after the reaction is finished to obtain a second intermediate; the ethylene carbonate xylene solution contains 64 mass percent of ethylene carbonate, the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution is 0.4mol, and the amount of potassium hydroxide is 2 mass percent of the propylene carbonate; the rate of dropping propylene carbonate and ethylene carbonate xylene solutions was 1 drop/second.
(3) Dissolving 0.001mol of the second intermediate obtained in the step (2) and potassium hydroxide in ethanol, heating to 80 ℃ in inert atmosphere (nitrogen atmosphere) mixing, slowly dropwise adding 3-chloro-2 hydroxy sodium propane sulfonate aqueous solution, reacting at constant temperature of 80 ℃ for 24 hours, and performing alcohol washing and separation to obtain an oilfield transition layer treating agent; the mass percentage of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 7.4%, the total amount of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 0.002mol, the mass ratio of the ethanol to the water contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 3.2:1, the dosage of the potassium hydroxide is 5.87% of the mass of the second intermediate used in the step (3), and the speed of dropwise adding the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 1 drop/second.
Structural analysis was performed on the initiator and the second intermediate obtained in example 1, and the results are shown in fig. 2 and 3; FIG. 2 is an infrared spectrum of the initiator in this example, wherein the initiator was measured at 3301cm -1 30cm at the point of treatment -1 Characteristic absorption peaks appearing at the positions are attributed to the absorption peaks of stretching vibration and bending vibration of the terminal primary amine; 1647cm -1 Characteristic absorption peaks at the points are attributed to telescopic vibration absorption peaks of-c=o; 1546cm -1 The coupling band of the bending vibration of the N-H bond and the stretching vibration of the C-N bond of-CONH-shows that the-CONH-exists in the molecule, which shows that N-dodecylamine reacts with methyl acrylate and ethylenediamine respectively to synthesize an initiator with an amino end group; FIG. 3 is an infrared spectrum of a second intermediate (hyperbranched polycarbonate) in this example, wherein at 3410cm -1 Characteristic absorption peak with hydroxyl nearby, 2980cm -1 And 2930cm -1 Nearby is-CH 2 Characteristic absorption peak, 1700cm -1 The vicinity is the characteristic absorption peak of carbonyl in-CONH-, 1690cm -1 Characteristic absorption peak of carbonyl in-COO-, 1480cm -1 And 1390cm -1 Characteristic adsorption peak of-CONH-, 1159cm -1 The characteristic adsorption peak of tertiary amine is 1125cm nearby -1 And 1060cm -1 The vicinity of the absorption peak is-C-O-C-characteristic, which shows that propylene carbonate, ethylene carbonate and an initiator react to form a block polymer containing ester groups, and hyperbranched polycarbonate is obtained.
Example 2
(1) Dissolving 0.02mol of n-dodecyl amine in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.08mol of methyl acrylate into the solution, then performing a first reaction at room temperature of 25 ℃ for 12 hours, and removing excessive methyl acrylate and methanol by reduced pressure distillation after the reaction is finished to obtain a first reaction product with an end group being an ester group, wherein in the first reaction, the dosage of the methanol accounts for 60% of the total mass of a first reaction system, and in the first reaction, the speed of dropwise adding the methyl acrylate is 1 drop/second; dissolving 0.01mol of the first reaction product in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.06mol of ethylenediamine into the reaction product, then performing a second reaction at room temperature of 25 ℃ for 12 hours, and removing excessive ethylenediamine and methanol by reduced pressure distillation after the reaction is finished to obtain an initiator with an amino end group, wherein the yield is 94.29%, the dosage of the methanol accounts for 69% of the total mass of a second reaction system in the second reaction, and the speed of dropwise adding the ethylenediamine is 1 drop/second in the second reaction.
(2) Mixing and heating 0.01mol of the initiator obtained in the step (1) and potassium hydroxide in an inert atmosphere (nitrogen atmosphere) to 100 ℃, slowly dropwise adding 0.2mol of propylene carbonate, and then carrying out constant temperature reaction for 2 hours at 110 ℃ to obtain a first intermediate; slowly dripping a vinyl carbonate xylene solution into the first intermediate, reacting for 2 hours at a constant temperature of 110 ℃, and cooling to room temperature after the reaction is finished to obtain a second intermediate; the ethylene carbonate xylene solution contains 64 mass percent of ethylene carbonate, the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution is 0.4mol, and the amount of potassium hydroxide is 2 mass percent of the propylene carbonate; the rate of dropping propylene carbonate and ethylene carbonate xylene solutions was 1 drop/second.
(3) Dissolving 0.001mol of the second intermediate obtained in the step (2) and potassium hydroxide in ethanol, heating to 70 ℃ in an inert atmosphere (nitrogen atmosphere), slowly dropwise adding a 3-chloro-2 hydroxy sodium propane sulfonate aqueous solution, reacting at a constant temperature of 70 ℃ for 18 hours, and performing alcohol washing and separation to obtain an oilfield transition layer treating agent; the mass percentage of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 7.4%, the total amount of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 0.002mol, the mass ratio of the ethanol to the water contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 3.2:1, the dosage of the potassium hydroxide is 5.87% of the mass of the second intermediate used in the step (3), and the speed of dropwise adding the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 1 drop/second.
Example 3
(1) Dissolving 0.02mol of n-octylamine in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.06mol of methyl acrylate into the solution, then performing a first reaction at room temperature of 25 ℃ for 18 hours, and removing excessive methyl acrylate and methanol by reduced pressure distillation after the reaction is finished to obtain a first reaction product with an end group being an ester group, wherein in the first reaction, the dosage of the methanol accounts for 67% of the total mass of a first reaction system, and in the first reaction, the speed of dropwise adding the methyl acrylate is 1 drop/second; dissolving 0.01mol of the first reaction product in methanol, introducing nitrogen to remove oxygen, then dropwise adding 0.08mol of ethylenediamine into the reaction product, then performing a second reaction at room temperature of 25 ℃ for 18 hours, and removing excessive ethylenediamine and methanol by reduced pressure distillation after the reaction is finished to obtain an initiator with an amino end group, wherein the yield is 95.12%, the dosage of the methanol accounts for 66% of the total mass of a second reaction system in the second reaction, and the speed of dropwise adding the ethylenediamine is 1 drop/second.
(2) Mixing and heating 0.01mol of the initiator obtained in the step (1) and potassium hydroxide in an inert atmosphere (nitrogen atmosphere) to 100 ℃, slowly dropwise adding 0.2mol of propylene carbonate, and then carrying out constant temperature reaction for 2 hours at 130 ℃ to obtain a first intermediate; slowly dripping a vinyl carbonate xylene solution into the first intermediate, reacting at the constant temperature of 130 ℃ for 2 hours, and cooling to room temperature after the reaction is finished to obtain a second intermediate; the ethylene carbonate xylene solution contains 64 mass percent of ethylene carbonate, the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution is 0.4mol, and the amount of potassium hydroxide is 2 mass percent of the propylene carbonate; the rate of dropping propylene carbonate and ethylene carbonate xylene solutions was 1 drop/second.
(3) Dissolving 0.001mol of the second intermediate obtained in the step (2) and sodium hydroxide in ethanol, heating to 60 ℃ in an inert atmosphere (nitrogen atmosphere), slowly dropwise adding a 3-chloro-2 hydroxy sodium propane sulfonate aqueous solution, reacting at a constant temperature of 60 ℃ for 24 hours, and performing alcohol washing and separation to obtain an oilfield transition layer treating agent; the mass percentage of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 7.4%, the total amount of the 3-chlorine-2 hydroxy sodium propane sulfonate contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 0.002mol, the mass ratio of ethanol to water contained in the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 3.2:1, the dosage of sodium hydroxide is 5% of the mass of the second intermediate used in the step (3), and the speed of dripping the 3-chlorine-2 hydroxy sodium propane sulfonate aqueous solution is 1 drop/second.
Example 4
Example 4 is substantially the same as example 1 except that:
in the step (2), the propylene carbonate was used in an amount of 0.05mol, and the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution was 0.15mol.
Example 5
Example 5 is substantially the same as example 1 except that:
in the step (2), the propylene carbonate was used in an amount of 0.5mol, and the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution was 1mol.
Example 6
Example 6 is substantially the same as example 1 except that:
in the step (3), the total amount of the 3-chloro-2-hydroxypropyl sodium sulfonate contained in the 3-chloro-2-hydroxypropyl sodium sulfonate aqueous solution is 0.0005mol.
Example 7
Example 7 is substantially the same as example 1 except that:
in the step (3), the total amount of 3-chloro-2-hydroxypropyl sodium sulfonate contained in the aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate was 0.0035mol.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that step (3) is not included and the second intermediate obtained in step (2) is directly used as an oilfield transition layer treatment agent.
Comparative example 2
Comparative example 1 is substantially the same as example 1 except that:
the step (2) is as follows: heating 0.01mol of the initiator obtained in the step (1) and potassium hydroxide to 100 ℃ in an inert atmosphere (nitrogen atmosphere), slowly dropwise adding 0.2mol of propylene carbonate, then carrying out constant temperature reaction for 4 hours at 120 ℃, and cooling to room temperature after the reaction is finished to obtain an intermediate; the dosage of the potassium hydroxide is 2% of the mass of the propylene carbonate; the speed of adding propylene carbonate dropwise is 1 drop/second; the intermediate obtained in this step (2) was used to replace the second intermediate in example 1 for the subsequent step (3).
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
(2) heating 0.01mol of the initiator obtained in the step (1) and potassium hydroxide to 100 ℃ in an inert atmosphere (nitrogen atmosphere), slowly dropwise adding a vinyl carbonate xylene solution, reacting at a constant temperature of 120 ℃ for 4 hours, and cooling to room temperature after the reaction is finished to obtain an intermediate; the ethylene carbonate xylene solution contains 64 mass percent of ethylene carbonate, the total amount of the ethylene carbonate contained in the ethylene carbonate xylene solution is 0.4mol, and the amount of potassium hydroxide is 2 mass percent of the ethylene carbonate contained in the ethylene carbonate xylene solution; the speed of dropping the ethylene carbonate xylene solution is 1 drop/second; the intermediate obtained in this step (2) was used to replace the second intermediate in example 1 for the subsequent step (3).
Comparative example 4
Example 3 of the referenced chinese patent application 2007101763518 synthesizes a demulsifier as an oilfield transition layer treatment agent.
The present invention conducted performance tests on the oilfield transition treatments prepared in examples 1 to 7 and comparative examples 1 to 4.
The first performance test method comprises the following steps: the ternary composite driving electro-dewatering sewage containing suspended solid particles is statically settled for 24 hours to obtain ternary composite driving electro-dewatering sewage with suspended solid particles basically removed, 80 g of ternary composite driving dewatering crude oil of Daqing oil field and 20 g of ternary composite driving electro-dewatering sewage after static settlement for 24 hours are added into a sample bottle at 50 ℃, emulsification is carried out in a high-speed shearing emulsifying machine for 5 minutes to obtain a simulated emulsion (simulated ternary composite driving produced liquid) with 20% of water content, an oilfield transition layer treating agent is added, the concentration (adding amount) of the oilfield transition layer treating agent is 600mg/L, after uniform mixing, the oilfield transition layer treating agent is placed into an electro-dewatering device, and the results of the volume compression rate, the current reduction and the water content in the oil phase of the transition layers corresponding to examples 1-7 and comparative examples 1-4 after electric dewatering for 30 minutes are shown in table 1; the invention also tests the change curves of the volume of the transition layer, the water content in the oil phase after the electric dehydration and the current value along with the concentration of the oilfield transition layer treating agent when the oilfield transition layer treating agent in the embodiment 1 of the invention is added into an electric dehydrator for treating the simulated emulsion according to the performance test method, and the results are respectively shown in figures 4 to 6; from fig. 4 to fig. 6, it is known that when the water content of the simulated ternary composite flooding produced fluid is 20%, the volume compression rate of the transition layer after the electrical stripping is up to 65% and the water content of the oil phase is reduced by 76% and the current amplitude reduction is up to 68% when the adding amount of the oil field transition layer treating agent is 600 mg/L.
The second performance test method is as follows: and (3) carrying out static sedimentation on ternary composite flooding electric-removal sewage containing suspended solid particles for 24 hours to obtain ternary composite flooding electric-removal sewage with suspended solid particles basically removed, adding 70 g of ternary composite flooding dehydrated crude oil of Daqing oil field and 30 g of ternary composite flooding electric-removal sewage after static sedimentation for 24 hours into a sample bottle at 50 ℃, emulsifying in a high-speed shearing emulsifying machine for 5 minutes to obtain a simulated emulsion (simulated ternary composite flooding produced liquid) with 30% of water content, adding an oilfield transition layer treating agent to enable the concentration (adding amount) of the oilfield transition layer treating agent to be 600mg/L, uniformly mixing, and placing the obtained mixture in an electric dehydrator to obtain the results of the volume compression rate of the transition layer, the current reduction amplitude and the water content in the oil phase corresponding to examples 1-3 after electric dehydration for 30 minutes, wherein the results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from the results in tables 1 and 2, the oilfield transition layer treating agent prepared by the invention has good effects of compressing the transition layer and reducing the current on the ternary composite flooding emulsion containing the transition layer, the oilfield transition layer treating agent obtained in some preferred embodiments can enable the volume compression rate of the transition layer to be more than 50%, the current reduction amplitude to be more than 45%, the water content of the treated crude oil to be reduced by more than 60%, especially for the simulated emulsion with the water content of 20%, the oilfield transition layer treating agent in embodiment 1 can enable the volume compression rate of the transition layer to be more than 65%, the current reduction amplitude to be more than 68%, the water content of the treated crude oil to be only 4.5%, and for the simulated emulsion with the water content of 30%, the oilfield transition layer treating agent in embodiment 3 can enable the volume compression rate of the transition layer to be more than 63%, the current reduction amplitude to be more than 64%, and the water content of the treated crude oil to be only 4.7%.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the oilfield transition layer treating agent, the preparation method and the application thereof disclosed in the embodiment of the invention are described in detail, and specific examples are applied to describe the embodiments of the invention, etc., and the description of the above examples is only used for helping to understand the method and the core idea of the invention; meanwhile, as one skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in summary; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing an oilfield transition layer treatment agent, which is characterized by comprising the following steps:
(1) Carrying out a first polymerization reaction on an initiator with an amino end group and propylene carbonate to obtain a first intermediate;
(2) Carrying out a second polymerization reaction on the first intermediate and ethylene carbonate to obtain a second intermediate;
(3) And (3) reacting the second intermediate with sodium chlorosulfonate to obtain the oilfield transition layer treating agent.
2. The method of manufacturing according to claim 1, characterized in that:
the molar ratio of the propylene carbonate to the initiator is (6-40): 1, a step of; and/or
The molar ratio of the ethylene carbonate to the initiator is (20-80): 1.
3. the method of manufacturing according to claim 1, characterized in that:
the first polymerization reaction and the second polymerization reaction are carried out under the action of a catalyst A, wherein the catalyst A is one or more of potassium hydroxide, potassium carbonate and triethylamine;
preferably, the catalyst A is used in an amount of 0.5 to 3% by mass of the propylene carbonate.
4. The method of manufacturing according to claim 1, characterized in that:
the temperature of the first polymerization reaction and/or the second polymerization reaction is 100-130 ℃ and the time is 2-6 h;
in step (2), the ethylene carbonate is added in the form of an ethylene carbonate solution;
preferably, the ethylene carbonate solution takes xylene and/or chlorobenzene as a solvent;
preferably, the ethylene carbonate solution contains 50 to 90 mass percent of ethylene carbonate.
5. The method of claim 1, wherein in step (3):
the reaction is carried out under the action of a catalyst B, wherein the catalyst B is potassium hydroxide and/or sodium hydroxide, and preferably, the dosage of the catalyst B is 2-8% of the mass of the second intermediate; and/or
The sodium chlorosulfonate is added in the form of a sodium chlorosulfonate aqueous solution, and preferably, the sodium chlorosulfonate aqueous solution contains 5-15% by mass of sodium chlorosulfonate.
6. The method of claim 1, wherein in step (3):
the sodium chlorosulfonate is sodium 2-chloroethyl sulfonate and/or sodium 3-chloro-2-hydroxy propane sulfonate;
the molar ratio of the sodium chlorosulfonate to the second intermediate is (1-3): 1, a step of;
in the step (3), the temperature of the reaction is 60-90 ℃, and the time of the reaction is 10-24 hours.
7. The preparation method according to any one of claims 1 to 6, wherein the preparation of the initiator comprises the steps of:
(a) Taking short-chain alcohol as a solvent, and enabling fatty amine and methyl acrylate to perform a first reaction to obtain a first reaction product;
(b) And (3) taking short-chain alcohol as a solvent, and carrying out a second reaction on the first reaction product and ethylenediamine to obtain the initiator with the end group of amino.
8. The method of manufacturing according to claim 7, wherein:
the first reaction and/or the second reaction is: reacting for 12-24 h at room temperature;
the molar ratio of the methyl acrylate to the fatty amine is (2-6): 1, a step of;
the mol ratio of the ethylenediamine to the fatty amine is (2-6): 1, a step of;
in the step (a) and/or the step (b), the dosage of the short-chain alcohol accounts for 60-90% of the total mass of the reaction system;
the fatty amine is C in alkyl chain 4 ～C 20 Preferably, the fatty amine is n-dodecyl amine and/or n-octyl amine; and/or
In step (a) and step (b), the short-chain alcohol is one or more of methanol, ethanol, n-propanol and isopropanol.
9. An oilfield transition layer treatment agent prepared by the method of any one of claims 1 to 8.
10. Use of an oilfield transition layer treatment agent prepared by the preparation method of any one of claims 1 to 8 for treating a ternary complex flooding produced fluid transition layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| US20090048352A1 (en) * | 2007-08-13 | 2009-02-19 | Ruela Talingting-Pabalan | Method for spearation crude oil emulsions |
| US20220213244A1 (en) * | 2019-09-24 | 2022-07-07 | Tianjin University | Novel demulsifier |
| CN115851281A (en) * | 2022-11-28 | 2023-03-28 | 大庆市富杰化工有限公司 | Naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| US20090048352A1 (en) * | 2007-08-13 | 2009-02-19 | Ruela Talingting-Pabalan | Method for spearation crude oil emulsions |
| US20220213244A1 (en) * | 2019-09-24 | 2022-07-07 | Tianjin University | Novel demulsifier |
| CN115851281A (en) * | 2022-11-28 | 2023-03-28 | 大庆市富杰化工有限公司 | Naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and preparation method thereof |
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