CN114426499A - Environment-triggered nitrogen-release type crude oil stripping agent, composition containing stripping agent and application of stripping agent - Google Patents
Environment-triggered nitrogen-release type crude oil stripping agent, composition containing stripping agent and application of stripping agent Download PDFInfo
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- 239000010779 crude oil Substances 0.000 title claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 230000001960 triggered effect Effects 0.000 title claims abstract description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003921 oil Substances 0.000 claims abstract description 42
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- -1 alkyl dicarboxylic acid Chemical compound 0.000 claims abstract description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000000295 fuel oil Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 20
- 238000004821 distillation Methods 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 7
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000006228 supernatant Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/04—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
Abstract
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to an environment-triggered nitrogen-release type crude oil stripping agent, a composition containing the stripping agent and an application of the stripping agent. The preparation method of the crude oil stripping agent comprises the following steps: in the presence of a catalyst, glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester; in a solvent 1, carrying out condensation reaction on the dibasic ester and hydrazine hydrate to obtain a product; and dissolving the product in a solvent 2, introducing chlorine gas to perform dehydrogenation reaction, then performing reduced pressure distillation, and performing vacuum drying to obtain the crude oil stripping agent. The composition consists of a crude oil stripping agent and sodium dodecyl benzene sulfonate, wherein the mass ratio of the crude oil stripping agent to the sodium dodecyl benzene sulfonate is (2-5):1, and more preferably 3: 1. The novel environment-triggered nitrogen release type crude oil stripping agent product can improve sweep efficiency and oil displacement efficiency, so that the recovery rate of thickened oil is improved. The field test can improve the recovery ratio by more than 15 percent.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to an environment-triggered nitrogen-release type crude oil stripping agent, a composition containing the stripping agent and an application of the stripping agent.
Background
The heavy oil is an important oil-gas resource in China, the geological reserve can reach 168.7 hundred million tons, and the heavy oil accounts for about half of the oil which is proved to be exploited in China. However, the viscosity of common thick oil is high, and the fluidity is poor, which brings great difficulty to the production process. The common means for improving the recovery ratio at the present stage are thermal recovery, steam stimulation and water drive cold recovery. The water flooding thickened oil is the most economic development mode at low oil price, and the leading technology is polymer flooding, viscosity reducer flooding and viscosity reduction composite flooding. The polymer flooding has the advantages of profile control, sweep improvement and the like, but the injection of the heavy oil reservoir is difficult when the concentration is too high; the injected concentration viscosity and the crude oil viscosity are often too different, so that the oil-water fluidity is larger than the oil-water fluidity, finger water channeling is formed during displacement, the injected water is in ineffective circulation, and the water drive recovery rate is low. The single viscosity reducer flooding can not improve the sweep efficiency of oil displacement, and the range of improving the recovery ratio is limited. The system with the viscosity reduction function and the spread efficiency is the current leading research and development direction, so the viscosity reduction composite flooding system is the current leading technology of a mine site. However, because the viscosity-reducing composite flooding is a bi-component system, the polymer and the viscosity reducer have certain chromatographic separation, and the oil displacement effect is inevitably influenced. If the system has a certain viscosity reduction effect and a certain microscopic wave efficiency enlarging system at the deep part of the stratum, the system is another effective way for improving the recovery efficiency of the water-drive thickened oil, and if the system can better strip the crude oil and improve the oil displacement efficiency while improving the wave, the system has more important significance for improving the recovery efficiency of the thickened oil.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide an environment-triggered nitrogen release type crude oil stripping agent, a composition containing the stripping agent and an application of the composition.
According to a first aspect of the invention, the invention discloses a preparation method of an environment-triggered nitrogen release type crude oil stripping agent, which comprises the following steps:
(1) in the presence of a catalyst, glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) in a solvent 1, carrying out condensation reaction on the dibasic ester and hydrazine hydrate to obtain a product;
(3) and (3) dissolving the product in a solvent 2, introducing chlorine gas to perform dehydrogenation reaction, distilling under reduced pressure, and drying in vacuum to obtain the crude oil stripping agent.
The structural general formula of the long-chain alkyl dicarboxylic acid is as follows:
wherein R is a normal or isomeric alkyl group of C10-C16, preferably a normal alkyl group of C12-C15.
According to a second aspect of the present invention, the present invention discloses a crude oil stripping agent prepared by the above method, wherein the crude oil stripping agent has the following structural formula:
wherein R is a normal or isomeric alkyl group of C10-C16, preferably a normal alkyl group of C12-C15.
According to a third aspect of the present invention, there is provided a composition comprising the above crude oil stripper, the composition consisting of a crude oil stripper and sodium dodecylbenzenesulfonate.
According to a fourth aspect of the invention, the invention discloses the use of the above composition in heavy oil recovery.
The crude oil stripping agent in the composition is partially attached to the surface of a rock oil film after being added into a heavy oil production layer, long-chain hydrophobic groups carried in molecules can invade into the oil film, nitrogen is released under the action of high temperature of a stratum, gemini surfactant is generated, the generated nitrogen is used as a gas driving force, the adhesion force of the rock oil film can be reduced through a disturbance effect, the low interfacial tension of the gemini surfactant is used for oil displacement, and the oil film can be rapidly stripped. The gas drive greatly improves the sweep efficiency, and the addition of the sodium dodecyl benzene sulfonate greatly improves the oil displacement efficiency.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the preparation method of the crude oil stripping agent comprises the steps of firstly carrying out esterification reaction on ethylene glycol and long-chain alkyl dicarboxylic acid to generate dibasic ester, then carrying out condensation reaction on the dibasic ester and hydrazine hydrate, then introducing chlorine gas to carry out oxidative dehydrogenation, and then blending with sodium dodecyl benzene sulfonate to improve the application range of the crude oil stripping agent.
(2) The preparation method of the crude oil stripping agent is simple and feasible, the product post-treatment is simpler, the industrial production is more suitable, and the prepared novel environment-triggered nitrogen release type crude oil stripping agent product can improve the sweep efficiency and the oil displacement efficiency, so that the recovery rate of the thickened oil is improved. The indoor oil displacement efficiency is improved by more than 50 percent, and the field test improves the recovery ratio by more than 15 percent.
Description of the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of the environmentally triggered nitrogen release type crude oil stripper obtained in example 3;
FIG. 2 is a graph showing a gas volume release test of the environmentally triggered nitrogen release type crude oil stripper obtained in example 3.
FIG. 3 is a graph showing the oil displacement effect of the environmentally triggered nitrogen release crude oil stripper product obtained in example 3.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the invention, the invention discloses a preparation method of an environment-triggered nitrogen release type crude oil stripping agent, which comprises the following steps:
(1) in the presence of a catalyst, glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) in a solvent 1, carrying out condensation reaction on the dibasic ester and hydrazine hydrate to obtain a product;
(3) and (3) dissolving the product in a solvent 2, introducing chlorine gas to perform dehydrogenation reaction, distilling under reduced pressure, and drying in vacuum to obtain the crude oil stripping agent.
The structural general formula of the long-chain alkyl dicarboxylic acid is as follows:
in the present invention, the ratio of the amounts of the long-chain alkyl dicarboxylic acid, the ethylene glycol and the hydrazine hydrate is preferably 2 (4-4.1): 1-1.1), and preferably 2 (4-4.05): 1-1.05).
Preferably, in the step (1), the catalyst is concentrated sulfuric acid or concentrated phosphoric acid, and the dosage of the concentrated sulfuric acid or concentrated phosphoric acid is 3-8%, preferably 5-6% of that of the ethylene glycol.
Preferably, in the step (1), the esterification reaction time is 1-2h, the reaction temperature is 140-150 ℃, and more preferably, the reaction time is 1-1.5h, and the reaction temperature is 140-145 ℃.
Preferably, in the step (1), the hydrazine hydrate is added for less than 1 h.
In the present invention, preferably, in the step (2), the solvent 1 is dimethyl sulfoxide or N, N-dimethylformamide, and the amount is 150 to 300% of the amount of ethylene glycol.
Preferably, in the step (2), the condensation reaction time is 1-1.5h, the reaction temperature is 25-30 ℃, and more preferably, the reaction time is 1-1.2h, and the reaction temperature is 25-28 ℃.
Preferably, the solvent 2 is one of dichloroethane, dichloromethane and ethyl acetate, and the dosage of the solvent is 100-300% of that of the glycol.
Preferably, the dehydrogenation reaction is carried out at a temperature of 25-30 ℃ for 2.5-3h, more preferably at a temperature of 26-28 ℃ for 2.7-3 h.
According to a more specific preferred embodiment, the preparation method of the crude oil stripping agent specifically comprises the following steps:
(1) placing ethylene glycol and long-chain alkyl dicarboxylic acid in a three-neck flask, slowly dropwise adding a catalyst, heating to 140-150 ℃, carrying out reflux reaction for 1-2h, after the reaction is finished, adding a saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with a saturated calcium chloride solution, standing, taking supernatant, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and the solvent 1 into a three-neck flask with a stirrer, stirring for 30-50min to fully dissolve, keeping the water bath temperature at 25-30 ℃, slowly dripping hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1-1.5h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in solvent 2, slowly introducing chlorine gas into the system, keeping the temperature of water bath at 25-30 ℃, reacting for 2.5-3h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
The crude oil stripping agent synthesis equation is as follows:
according to a second aspect of the present invention, the present invention discloses a crude oil stripping agent prepared by the above method, wherein the crude oil stripping agent has the following structural formula:
wherein R is a normal or isomeric alkyl group of C10-C16, preferably a normal alkyl group of C12-C15.
According to a third aspect of the present invention, there is provided a composition comprising the above crude oil stripper, the composition consisting of a crude oil stripper and sodium dodecylbenzenesulfonate.
Preferably, the mass ratio of the crude oil stripping agent to the dodecylbenzene sulfonic acid is (2-5):1, and more preferably 3: 1.
The invention discloses a crude oil stripping agent prepared by the method, which has the following structural formula:
according to a fourth aspect of the invention, the invention discloses the use of the above composition in heavy oil recovery.
Preferably, the application is particularly the application of the oil film stripping agent in heavy oil recovery.
The specific application process is not particularly required, and can be a conventional application mode in the field, and the detailed description is omitted here.
The environment-triggered nitrogen-release type crude oil stripping agent in the composition can be partially attached to the surface of a rock oil film after being added into a heavy oil production layer, long-chain hydrophobic groups carried in molecules can invade into the oil film, nitrogen is released under the action of high temperature of a stratum, gemini surfactants are generated, the generated nitrogen is used as a gas driving force, the adhesion force of the rock oil film can be reduced through a disturbance effect, the low interfacial tension of the gemini surfactants is used for oil displacement, and the oil film can be rapidly stripped. The gas drive greatly improves the sweep efficiency, and the addition of the sodium dodecyl benzene sulfonate greatly improves the oil displacement efficiency. The principle is realized by the following reaction:
the preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The present invention will be further described with reference to specific examples.
In the present invention, the apparatus or equipment used is a conventional apparatus or equipment known in the art, and is commercially available.
In the following examples and comparative examples, the reagents used are all chemically pure reagents from commercial sources, unless otherwise specified.
Example 1
(1) Placing 23g of dodecyl diacid and 46g of ethylene glycol in a three-neck flask, slowly dropwise adding 1.38g of concentrated sulfuric acid as a catalyst, heating to 140 ℃, carrying out reflux reaction for 1h, after the reaction is finished, adding 10ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 20ml of saturated calcium chloride solution, standing, taking supernatant, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 69g of dimethyl sulfoxide into a three-neck flask with a stirrer, stirring for 30min to fully dissolve, keeping the water bath temperature at 25 ℃, slowly dropwise adding 11.5g of hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 46g of dichloromethane, slowly introducing chlorine gas into the system, keeping the temperature of a water bath at 25 ℃, reacting for 2.5h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
Blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 3:1 to obtain the composition.
Example 2
(1) Placing 23g of dodecyl diacid and 46.12g of ethylene glycol in a three-neck flask, slowly dropwise adding 1.85g of concentrated sulfuric acid as a catalyst, heating to 150 ℃, carrying out reflux reaction for 2 hours, after the reaction is finished, adding 20ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 20ml of saturated calcium chloride solution, standing, taking supernatant, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 80g N, N-dimethylformamide into a three-neck flask with a stirrer, stirring for 40min to fully dissolve, keeping the water bath temperature at 30 ℃, slowly dropwise adding 11.8g of hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1.5h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 100g of dichloromethane, slowly introducing chlorine gas into the system, keeping the temperature of a water bath at 30 ℃, reacting for 2.6h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
And blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 5:1 to obtain a final product.
Example 3
(1) Placing 23g of dodecyl diacid and 46.35g of ethylene glycol in a three-neck flask, slowly dropwise adding 2.32g of concentrated sulfuric acid as a catalyst, heating to 142 ℃, carrying out reflux reaction for 1.2h, after the reaction is finished, adding 15ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 30ml of saturated calcium chloride solution, standing, taking supernatant, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 95.2g of dimethyl sulfoxide into a three-neck flask with a stirrer, stirring for 35min to fully dissolve, keeping the water bath temperature at 26 ℃, slowly dropwise adding 11.95g of hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1.2h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 90.2g dichloroethane, slowly introducing chlorine into the system, keeping the temperature of the water bath at 30 ℃, reacting for 3h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
And blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 3:1 to obtain a final product.
Example 4
(1) Placing 23g of dodecyl diacid and 46.58g of ethylene glycol in a three-neck flask, slowly dropwise adding 2.79g of concentrated phosphoric acid as a catalyst, heating to 145 ℃, carrying out reflux reaction for 1.5h, after the reaction is finished, adding 20ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 30ml of saturated calcium chloride solution, taking supernatant after standing, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 102.8g N, N-dimethylformamide into a three-neck flask with a stirrer, stirring for 40min to fully dissolve, keeping the water bath temperature at 25 ℃, slowly adding 12.02g of hydrazine hydrate dropwise into the three-neck flask within 1h, continuing to react for 1.3h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 120g dichloroethane, slowly introducing chlorine into the system, keeping the water bath temperature at 28 ℃, reacting for 2.5h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
And blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 4:1 to obtain a final product.
Example 5
(1) Placing 23g of dodecyl diacid and 47.15g of ethylene glycol in a three-neck flask, slowly dropwise adding 3.3g of concentrated phosphoric acid as a catalyst, heating to 148 ℃, carrying out reflux reaction for 1.8h, after the reaction is finished, adding 10ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 30ml of saturated calcium chloride solution, taking supernatant after standing, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 118.7g of dimethyl sulfoxide into a three-neck flask with a stirrer, stirring for 50min to fully dissolve, keeping the water bath temperature at 27 ℃, slowly dropwise adding 12.25g of hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1.1h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 130g of ethyl acetate, slowly introducing chlorine gas into the system, keeping the temperature of a water bath at 27 ℃, reacting for 2.7h, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
And blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 2:1 to obtain a final product.
Example 6
(1) Placing 23g of dodecyl diacid and 46.86g of ethylene glycol in a three-neck flask, slowly dropwise adding 3.74g of concentrated phosphoric acid as a catalyst, heating to 143 ℃, carrying out reflux reaction for 1.2h, after the reaction is finished, adding 30ml of saturated sodium chloride solution, fully shaking, pouring into a separating funnel, standing for layering, taking supernatant, washing with 30ml of saturated calcium chloride solution, taking supernatant after standing, and carrying out reduced pressure distillation to obtain the dibasic ester.
(2) And adding the dibasic ester and 140.58g N, N-dimethylformamide into a three-neck flask with a stirrer, stirring for 50min to fully dissolve, keeping the water bath temperature at 26 ℃, slowly dropwise adding 12.65g of hydrazine hydrate into the three-neck flask within 1h, continuously reacting for 1.3h, and distilling under reduced pressure after the reaction is finished to obtain the product.
(3) Dissolving the obtained product in 135g of ethyl acetate, slowly introducing chlorine gas into the system, keeping the temperature of a water bath at 28 ℃, reacting for 3 hours, distilling the liquid under reduced pressure after the reaction is finished, and drying in vacuum to obtain the crude oil stripping agent.
And blending the crude oil stripping agent and sodium dodecyl benzene sulfonate according to the mass ratio of 3:1 to obtain a final product.
Test example 1 nuclear magnetic hydrogen spectrum test
In order to characterize the structural characteristics of the novel environmental-triggered nitrogen release type crude oil stripping agent, the sample in example 3 was subjected to nuclear magnetic hydrogen spectroscopy, and the results are shown in fig. 1. FIG. 1 is the nuclear magnetic hydrogen spectrum of the novel environmental-triggered nitrogen release type crude oil stripper obtained in example 3.
1H NMR(300MHz，DMSO)：δ4.89(s，2H)，4.22(t，4H)，4.1(t，4H)，3.54(t，4H)，2.32(t，8H)，1.79(t，4H)，1.66(m，8H)，1.33-1.26(m，24H)ppm。
Test example 2 gas Release Performance test
50g of the novel environment-triggered nitrogen release type crude oil stripping agent product is weighed in a three-neck flask, heated in a water bath, and the volume of nitrogen gas released by 50g of the product is measured by a drainage method and compared with the theoretical release amount, as shown in figure 2. As can be seen from the figure, the nitrogen release in the system gradually increases with increasing temperature, reaching a peak at 80-90 ℃ and releasing 48% of the theoretical volume of nitrogen.
Test example 3 oil displacement Performance test
The oil displacement performance of the novel environment-triggered nitrogen release type crude oil stripping agent product is tested through a static capillary oil displacement experiment. The specific process of the experiment is as follows: and (3) immersing a capillary tube (the diameter is 0.3mm) into the thick oil, taking out after the thick oil is fully absorbed, wiping the capillary tube clean, and putting the capillary tube into a sample bottle filled with the product solution. Then placing the sample bottle into an oven, heating to 80 ℃, regularly observing and recording the condition of crude oil driven out of the capillary tube, as shown in figure 3; FIG. 3 shows the oil displacement effect of the novel environmentally triggered nitrogen release type crude oil stripper product.
Wherein m is0Mass of capillary tube, m1The mass of the capillary full of the thickened oil is shown, and m is the mass of the capillary after oil displacement.
The effect before and after oil displacement is obvious, and the oil displacement effect is more obvious along with the increase of the use concentration. When the use concentration is 0.5%, the oil displacement rate can reach 75%.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (17)
1. The preparation method of the environment-triggered nitrogen release type crude oil stripping agent is characterized by comprising the following steps of:
(1) in the presence of a catalyst, glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) in a solvent 1, carrying out condensation reaction on the dibasic ester and hydrazine hydrate to obtain a product;
(3) and (3) dissolving the product in a solvent 2, introducing chlorine gas to perform dehydrogenation reaction, distilling under reduced pressure, and drying in vacuum to obtain the crude oil stripping agent.
2. The method according to claim 1, wherein the mass ratio of the long-chain alkyl dicarboxylic acid, the ethylene glycol and the hydrazine hydrate is 2 (4-4.1) to (1-1.1).
3. The method according to claim 2, wherein the mass ratio of the long-chain alkyl dicarboxylic acid, the ethylene glycol and the hydrazine hydrate is 2 (4-4.05) to (1-1.05).
4. The method of claim 1, wherein the catalyst is concentrated sulfuric acid or concentrated phosphoric acid in an amount of 3-8% of the amount of ethylene glycol.
5. The preparation method according to claim 1, wherein the esterification reaction time is 1-2h, and the reaction temperature is 140-150 ℃.
6. The preparation method according to claim 5, wherein the esterification reaction time is 1-1.5h, and the reaction temperature is 140-145 ℃.
7. The method according to claim 1, wherein the solvent 1 is dimethyl sulfoxide or N, N-dimethylformamide in an amount of 150-300% based on ethylene glycol.
8. The preparation method according to claim 1, wherein the condensation reaction time is 1-1.5h, and the reaction temperature is 25-30 ℃.
9. The method according to claim 8, wherein the condensation reaction time is 1-1.2h and the reaction temperature is 25-28 ℃.
10. The preparation method according to claim 1, wherein the solvent 2 is one of dichloroethane, dichloromethane and ethyl acetate, and the amount of the solvent is 100-300% of the amount of the glycol.
11. The method according to claim 1, wherein the dehydrogenation reaction is carried out at a temperature of 25 to 30 ℃ for a reaction time of 2.5 to 3 hours.
12. The method according to claim 11, wherein the dehydrogenation reaction is carried out at a temperature of 26 to 28 ℃ for a time of 2.7 to 3 hours.
13. The crude oil stripper as prepared by the preparation method of any one of claims 1-12, wherein the crude oil stripper has the following structural formula:
wherein R is a normal or isomeric alkyl of C10-C16.
14. The composition comprising the crude oil stripper of claim 13, wherein the composition further comprises sodium dodecylbenzene sulfonate.
15. The composition as claimed in claim 14, wherein the mass ratio of the crude oil stripping agent to the dodecylbenzene sulfonic acid is (2-5): 1.
16. Use of a composition according to any one of claims 14 to 15 in heavy oil recovery.
17. Use according to claim 16, wherein the composition is used as an oil film stripper in heavy oil recovery.
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