CN114426499B - 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 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- 230000001960 triggered effect Effects 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003921 oil Substances 0.000 claims abstract description 48
- 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 23
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 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
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 13
- -1 alkyl dicarboxylic acid Chemical compound 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- 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 5
- 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
- 238000000034 method Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 abstract description 20
- 238000004821 distillation Methods 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 8
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 abstract 1
- 229940071161 dodecylbenzenesulfonate Drugs 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
- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 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
- 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 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
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect 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
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000003208 petroleum Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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 application thereof. The preparation method of the crude oil stripping agent comprises the following steps: in the presence of a catalyst, the glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester; in a solvent 1, the dibasic ester and hydrazine hydrate are subjected to condensation reaction to obtain a product; dissolving the product in a solvent 2, introducing chlorine 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 dodecyl benzene sulfonate is (2-5): 1, more preferably 3:1. The novel environment-triggered nitrogen release type crude oil stripping agent product can improve the sweep efficiency and the oil displacement efficiency, thereby improving the recovery rate of thick oil. The field test improves 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 application thereof.
Background
Thickened oil is an important oil gas resource in China, and the geological reserve can reach 168.7 hundred million tons, which accounts for about half of the well-proven petroleum in China. However, the conventional thick oil has relatively high viscosity and relatively poor fluidity, which makes the exploitation process very difficult. The means of improving recovery efficiency commonly used at the present stage are thermal recovery, steam huff and puff and water drive cold recovery. The water-driven thickened oil is the most economical development mode under low oil price, and the dominant technology is polymer driving, viscosity reducer driving and viscosity reduction compound driving. Polymer flooding has the advantages of profile control, improvement, and the like, but the injection of a heavy oil reservoir is difficult when the concentration is too high; the injected concentration viscosity and the crude oil viscosity often have too great difference, so that the oil-water fluidity is relatively large, and the injected water is ineffective and circulated due to the formation of finger-water channeling during displacement, so that the water flooding recovery ratio is low. The sweep efficiency of oil displacement cannot be improved by using a single viscosity reducer, and the range of improving the recovery ratio is limited. The viscosity reduction compound flooding system has the viscosity reduction effect, and simultaneously has the system for expanding the sweep efficiency, which is the current dominant research and development direction, so that the viscosity reduction compound flooding system is the current technology of mine dominance. However, because the viscosity reduction composite flooding is a bi-component system, certain chromatographic separation exists between the polymer and the viscosity reducer, and the flooding effect is necessarily affected. If the viscosity reduction effect is achieved, a system for enlarging microscopic sweep efficiency is achieved at the deep part of the stratum, the viscosity reduction effect is achieved, the system is an effective way for improving the recovery ratio of water-driven thickened oil, meanwhile, if the system can strip crude oil better while sweep is improved, the viscosity reduction effect is achieved, and the viscosity reduction effect is achieved.
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 application thereof, wherein the composition is added to a thick oil exploitation layer, and then part of the composition is adhered to the surface of a rock oil film, and is decomposed to generate gas and surfactant under the action of high-temperature environment of a ground layer, so that the rapid stripping of the thick oil film is realized under the action of gas driving and surfactant low interfacial tension oil displacement, and the subsequent gas also plays a role of expanding microscopic wave and volume to a certain extent, thereby improving the recovery ratio of thick oil.
According to a first aspect of the invention, the invention discloses a preparation method of an environment-triggered nitrogen release crude oil stripping agent, which comprises the following steps:
(1) In the presence of a catalyst, the glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) In a solvent 1, the dibasic ester and hydrazine hydrate are subjected to condensation reaction to obtain a product;
(3) Dissolving the product in a solvent 2, introducing chlorine gas for 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 C10-C16 normal or isomeric alkyl radical, preferably a C12-C15 normal alkyl radical.
According to a second aspect of the present invention, the present invention discloses a crude oil stripper prepared by the above method, wherein the crude oil stripper has the following structural formula:
wherein R is a C10-C16 normal or isomeric alkyl radical, preferably a C12-C15 normal alkyl radical.
According to a third aspect of the present invention there is provided a composition comprising the crude oil stripper as described above, the composition consisting of a crude oil stripper and sodium dodecylbenzene sulfonate.
According to a fourth aspect of the present invention, the use of the above composition in heavy oil recovery is disclosed.
The crude oil stripping agent in the composition disclosed by the invention is partially attached to the surface of a rock oil film after being added into a thick oil exploitation layer, long-chain hydrophobic groups carried in molecules can invade the oil film, nitrogen is released under the high-temperature action of a stratum, a gemini surfactant is generated, the generated nitrogen is used as a gas driving force to reduce the adhesion force of the rock oil film through the disturbance action, oil displacement is carried out by virtue of low interfacial tension of the gemini surfactant, and the rapid stripping of the oil film can be realized. The sweep efficiency is greatly improved by gas driving, and the oil displacement efficiency is greatly improved by adding sodium dodecyl benzene sulfonate.
Compared with the prior art, the invention has the beneficial effects and advantages that:
(1) The crude oil stripping agent is prepared through esterification of glycol and long-chain alkyl dicarboxylic acid to produce dibasic ester, condensation of dibasic ester and hydrazine hydrate, oxidative dehydrogenation with chlorine, and blending with sodium dodecyl benzene sulfonate.
(2) The preparation method of the crude oil stripping agent is simple and feasible, the post-treatment of the product is simpler, the method is more suitable for industrial production, and the prepared novel environment-triggered nitrogen release type crude oil stripping agent product can improve the sweep efficiency and the oil displacement efficiency, thereby improving the recovery rate of thick oil. The indoor oil displacement efficiency is improved by more than 50%, and the recovery ratio is improved by more than 15% through field test.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance spectrum of the environment-triggered nitrogen release crude oil stripper obtained in example 3;
FIG. 2 is a graph showing the gas volume release test of the environment-triggered nitrogen-releasing crude oil stripping agent obtained in example 3.
FIG. 3 is a graph showing the displacement effect of the environmentally triggered nitrogen release crude oil stripper product obtained in example 3.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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 crude oil stripping agent, which comprises the following steps:
(1) In the presence of a catalyst, the glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) In a solvent 1, the dibasic ester and hydrazine hydrate are subjected to condensation reaction to obtain a product;
(3) Dissolving the product in a solvent 2, introducing chlorine gas for 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 invention, the mass ratio of the long-chain alkyl dicarboxylic acid, the ethylene glycol and the hydrazine hydrate is preferably 2 (4-4.1): 1-1.1, preferably 2 (4-4.05): 1-1.05.
Preferably, in step (1), the catalyst is concentrated sulfuric acid or concentrated phosphoric acid, and the amount of the catalyst is 3-8%, preferably 5-6% of the amount of ethylene glycol.
Preferably, in step (1), the esterification reaction time is 1 to 2 hours, the reaction temperature is 140 to 150 ℃, more preferably, the reaction time is 1 to 1.5 hours, and the reaction temperature is 140 to 145 ℃.
Preferably, in the step (1), the hydrazine hydrate is added for less than 1h.
In the present invention, preferably, in the step (2), the solvent 1 is dimethyl sulfoxide or N, N-dimethylformamide, and the amount of the solvent is 150-300% of the amount of ethylene glycol.
Preferably, in step (2), the condensation reaction time is 1 to 1.5 hours, the reaction temperature is 25 to 30 ℃, more preferably, the reaction time is 1 to 1.2 hours, and the reaction temperature is 25 to 28 ℃.
Preferably, the solvent 2 is one of dichloroethane, dichloromethane and ethyl acetate, and the dosage is 100-300% of the dosage of ethylene glycol.
Preferably, the dehydrogenation reaction is carried out at a temperature of 25-30 ℃ for a reaction time of 2.5-3 hours, more preferably at a temperature of 26-28 ℃ for a reaction time of 2.7-3 hours.
According to a more specific preferred embodiment, the method for preparing 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, adding a saturated sodium chloride solution into the mixture after the reaction is finished, fully shaking the mixture, pouring the mixture into a separating funnel, standing the mixture for layering, washing supernatant with a saturated calcium chloride solution, standing the mixture, and taking supernatant for reduced pressure distillation to obtain dibasic ester.
(2) Adding the dibasic ester and the solvent 1 into a three-neck flask with a stirrer, keeping the water bath temperature at 25-30 ℃ after stirring for 30-50min for full dissolution, slowly dripping hydrazine hydrate into the three-neck flask within 1h, continuing to react for 1-1.5h, and performing reduced pressure distillation after the reaction is finished to obtain a product.
(3) Dissolving the obtained product in a solvent 2, slowly introducing chlorine into the system, keeping the water bath temperature at 25-30 ℃, reacting for 2.5-3h, distilling the liquid under reduced pressure after the reaction is finished, and vacuum drying 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 stripper prepared by the above method, wherein the crude oil stripper has the following structural formula:
wherein R is a C10-C16 normal or isomeric alkyl radical, preferably a C12-C15 normal alkyl radical.
According to a third aspect of the present invention there is provided a composition comprising the crude oil stripper as described above, the composition consisting of a crude oil stripper and sodium dodecylbenzene sulfonate.
Preferably, the crude oil stripper and dodecylbenzene sulfonic acid are present in a mass ratio of (2-5): 1, 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 present invention, the use of the above composition in heavy oil recovery is disclosed.
Preferably, the application is specifically the application of the oil film stripping agent in the exploitation of thick oil.
The specific application process is not particularly required, and can be a conventional application mode in the field, and is not further described herein.
The environment-triggered nitrogen release type crude oil stripping agent in the composition disclosed by the invention is partially attached to the surface of a rock oil film after being added into a thick oil exploitation layer, long-chain hydrophobic groups carried in molecules can invade the inside of the oil film, nitrogen is released under the high-temperature action of a stratum, a gemini surfactant is generated, the generated nitrogen is used as a gas driving force to reduce the adhesion force of the rock oil film through the disturbance action, oil displacement is carried out by the gemini surfactant with low interfacial tension, and the rapid stripping of the oil film can be realized. The sweep efficiency is greatly improved by gas driving, and the oil displacement efficiency is greatly improved by adding sodium dodecyl benzene sulfonate. The principle is realized through the following reactions:
the preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
The invention will be further illustrated with reference to specific examples.
In the present invention, the devices or apparatus used are all conventional devices or apparatus known in the art, and are commercially available.
In the following examples and comparative examples, each reagent used was a chemically pure reagent from commercial sources, unless otherwise specified.
Example 1
(1) 23g of dodecyl diacid and 46g of ethylene glycol are placed in a three-neck flask, 1.38g of concentrated sulfuric acid is slowly added dropwise as a catalyst, the temperature is raised to 140 ℃, the reflux reaction is carried out for 1h, 10ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is fully shaken and poured into a separating funnel, the mixture is kept stand for layering, the supernatant is taken and washed by 20ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain the dibasic ester.
(2) Adding the dibasic ester and 69g of dimethyl sulfoxide into a three-neck flask with a stirrer, keeping the water bath temperature at 25 ℃ after stirring for 30min for full dissolution, slowly dripping 11.5g of hydrazine hydrate into the three-neck flask within 1h, continuing to react for 1h, and distilling under reduced pressure after the reaction is finished to obtain a product.
(3) Dissolving the obtained product in 46g of dichloromethane, slowly introducing chlorine into the system, keeping the water bath temperature at 25 ℃, reacting for 2.5h, distilling the liquid under reduced pressure after the reaction is finished, and vacuum drying 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) 23g of dodecyl diacid and 46.12g of ethylene glycol are placed in a three-neck flask, 1.85g of concentrated sulfuric acid is slowly added dropwise as a catalyst, the temperature is raised to 150 ℃, the reflux reaction is carried out for 2 hours, 20ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is poured into a separating funnel after full shaking, the mixture is stood for layering, the supernatant is taken and washed by 20ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain dibasic ester.
(2) Adding the dibasic ester and 80g of N, N-dimethylformamide into a three-neck flask with a stirrer, keeping the water bath temperature at 30 ℃ after stirring for 40min to fully dissolve, slowly dropwise adding 11.8g of hydrazine hydrate into the three-neck flask within 1h, continuing to react for 1.5h, and performing reduced pressure distillation after the reaction is finished to obtain a product.
(3) Dissolving the obtained product in 100g of dichloromethane, slowly introducing chlorine into the system, keeping the water bath temperature at 30 ℃, reacting for 2.6h, distilling the liquid under reduced pressure after the reaction is finished, and vacuum drying to obtain the crude oil stripping agent.
And (3) 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) 23g of dodecyl diacid and 46.35g of ethylene glycol are placed in a three-neck flask, 2.32g of concentrated sulfuric acid is slowly added dropwise as a catalyst, the temperature is raised to 142 ℃, the reflux reaction is carried out for 1.2h, 15ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is poured into a separating funnel after full shaking, the mixture is placed still for layering, the supernatant is taken and washed by 30ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain dibasic ester.
(2) Adding the diester and 95.2g of dimethyl sulfoxide into a three-neck flask with a stirrer, keeping the water bath temperature at 26 ℃ after stirring for 35min to fully dissolve, slowly adding 11.95g of hydrazine hydrate dropwise into the three-neck flask within 1h, continuing to react for 1.2h, and distilling under reduced pressure after the reaction is finished to obtain a product.
(3) Dissolving the obtained product in 90.2g of dichloroethane, slowly introducing chlorine into the system, keeping the water bath temperature at 30 ℃, reacting for 3 hours, distilling the liquid under reduced pressure after the reaction is finished, and vacuum drying to obtain the crude oil stripping agent.
And (3) 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) 23g of dodecyl diacid and 46.58g of ethylene glycol are placed in a three-neck flask, 2.79g of concentrated phosphoric acid is slowly added dropwise as a catalyst, the temperature is raised to 145 ℃, the reflux reaction is carried out for 1.5h, 20ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is poured into a separating funnel after full shaking, the mixture is placed still for layering, the supernatant is taken and washed by 30ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain dibasic ester.
(2) Adding the dibasic ester and 102.8g of N, N-dimethylformamide into a three-neck flask with a stirrer, keeping the water bath temperature at 25 ℃ after stirring for 40min to fully dissolve, slowly dripping 12.02g of hydrazine hydrate 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 of 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 vacuum drying to obtain the crude oil stripping agent.
And (3) 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) 23g of dodecyl diacid and 47.15g of ethylene glycol are placed in a three-neck flask, 3.3g of concentrated phosphoric acid is slowly added dropwise as a catalyst, the temperature is raised to 148 ℃, the reflux reaction is carried out for 1.8h, 10ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is poured into a separating funnel after full shaking, the mixture is placed still for layering, the supernatant is taken and washed by 30ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain dibasic ester.
(2) Adding the dibasic ester and 118.7g of dimethyl sulfoxide into a three-neck flask with a stirrer, keeping the water bath temperature at 27 ℃ after stirring for 50min to fully dissolve, slowly dripping 12.25g of hydrazine hydrate into the three-neck flask within 1h, continuing to react for 1.1h, and distilling under reduced pressure after the reaction is finished to obtain a product.
(3) Dissolving the obtained product in 130g of ethyl acetate, slowly introducing chlorine into the system, keeping the water bath temperature at 27 ℃, reacting for 2.7h, distilling the liquid under reduced pressure after the reaction is finished, and vacuum drying to obtain the crude oil stripping agent.
And (3) 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) 23g of dodecyl diacid and 46.86g of ethylene glycol are placed in a three-neck flask, 3.74g of concentrated phosphoric acid is slowly added dropwise as a catalyst, the temperature is raised to 143 ℃, the reflux reaction is carried out for 1.2h, 30ml of saturated sodium chloride solution is added into the mixture after the reaction is finished, the mixture is poured into a separating funnel after full shaking, the mixture is placed still for layering, the supernatant is taken and washed by 30ml of saturated calcium chloride solution, and the supernatant is taken for reduced pressure distillation after the standing, so as to obtain dibasic ester.
(2) Adding the dibasic ester and 140.58g of N, N-dimethylformamide into a three-neck flask with a stirrer, keeping the water bath temperature at 26 ℃ after stirring for 50min to fully dissolve, slowly dripping 12.65g of hydrazine hydrate 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 a product.
(3) Dissolving the obtained product in 135g of ethyl acetate, slowly introducing chlorine into the system, keeping the water bath temperature 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 (3) 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 Spectrometry test
To characterize the structural characteristics of the novel environment-triggered nitrogen release crude oil stripper, a nuclear magnetic hydrogen spectrum test was performed on the sample in example 3, and the results are shown in fig. 1. FIG. 1 is a nuclear magnetic resonance spectrum of the novel environment-triggered nitrogen release crude oil stripping agent obtained in example 3.
1 H 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 crude oil stripping agent product is weighed into a three-neck flask, heated in a water bath, and the volume of nitrogen gas released by 50g of the novel environment-triggered nitrogen release crude oil stripping agent 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 graph, the release amount of nitrogen in the system gradually increases with the rise of the temperature, reaches a peak value at 80-90 ℃ and can release 48% of theoretical volume of nitrogen.
Test example 3 oil displacement performance test
The oil displacement performance of the novel environment-triggered nitrogen release crude oil stripping agent product is tested through a static capillary oil displacement experiment. The specific procedure of the experiment is as follows: immersing capillary (diameter of 0.3 mm) in thick oil, taking out after sucking the thick oil, wiping, and placing into a sample bottle containing the product solution. Then the sample bottle is put into an oven to be heated to 80 ℃, and the condition of crude oil driving out of a capillary tube is observed and recorded at regular time, as shown in figure 3; FIG. 3 is a graph showing the displacement of oil from a novel environmentally triggered nitrogen release crude oil stripper product.
Wherein m is 0 For the mass of the capillary, m 1 The mass of the capillary tube filled with thick oil is the mass of the capillary tube after oil displacement.
The graph shows that the oil displacement effect is quite obvious before and after oil displacement, and the oil displacement effect is more obvious along with the increase of the use concentration. When the concentration is 0.5%, the oil displacement rate can reach 75%.
The foregoing is a further elaboration of the present invention, and it is not intended that the invention be limited to the specific embodiments shown, but rather that a number of simple deductions or substitutions be made by one of ordinary skill in the art without departing from the spirit of the invention, all shall be deemed to fall within the scope of the invention as defined by the claims which are filed herewith.
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, the glycol and long-chain alkyl dicarboxylic acid are subjected to esterification reaction to generate dibasic ester;
(2) In a solvent 1, the dibasic ester and hydrazine hydrate are subjected to condensation reaction to obtain a product;
(3) Dissolving the product in a solvent 2, introducing chlorine gas for dehydrogenation reaction, distilling under reduced pressure, and vacuum drying to obtain the crude oil stripping agent, wherein the crude oil stripping agent has the following structural formula:
wherein R is a C10-C16 normal or isomeric alkyl radical.
2. The preparation 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): 1-1.1.
3. The preparation 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): 1-1.05.
4. The preparation method according to claim 1, wherein the catalyst is concentrated sulfuric acid or concentrated phosphoric acid, and the amount of the catalyst is 3-8% of the amount of ethylene glycol.
5. The process according to claim 1, wherein the esterification reaction time is 1 to 2 hours and the reaction temperature is 140 to 150 ℃.
6. The process according to claim 5, wherein the esterification reaction time is 1 to 1.5 hours and the reaction temperature is 140 to 145 ℃.
7. The preparation method according to claim 1, wherein the solvent 1 is dimethyl sulfoxide or N, N-dimethylformamide, and the dosage is 150-300% of the dosage of ethylene glycol.
8. The process according to claim 1, wherein the condensation reaction time is 1 to 1.5 hours and the reaction temperature is 25 to 30 ℃.
9. The process of claim 8, wherein the condensation reaction time is 1 to 1.2 hours and the reaction temperature is 25 to 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 ethylene glycol.
11. The process of claim 1, wherein the dehydrogenation is carried out at a temperature of 25 to 30℃for a period of 2.5 to 3 hours.
12. The process of claim 11, wherein the dehydrogenation is carried out at a temperature of 26-28 ℃ for a period of 2.7-3 hours.
13. The crude oil remover manufactured by the manufacturing method as claimed in any one of claims 1 to 12, wherein the crude oil remover has the following structural formula:
wherein R is a C10-C16 normal or isomeric alkyl radical.
14. A composition comprising the crude oil stripper of claim 13, wherein the composition further comprises sodium dodecylbenzene sulfonate.
15. The composition of claim 14, wherein the crude oil stripper and dodecylbenzene sulfonic acid are present in a mass ratio of (2-5): 1.
16. Use of a composition according to any one of claims 14-15 in heavy oil recovery.
17. The use according to claim 16, characterized in that the composition is used as an oil film stripper in heavy oil recovery.
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| US4813484A (en) * | 1987-12-28 | 1989-03-21 | Mobil Oil Corporation | Chemical blowing agents for improved sweep efficiency |
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| CN101326144A (en) * | 2005-11-15 | 2008-12-17 | 金斯顿女王大学 | Reversibly switchable surfactants and methods of use thereof |
| CN102061158A (en) * | 2010-11-26 | 2011-05-18 | 华鼎鸿基采油技术服务（北京）有限公司 | Foam reinforcing polymer oil displacement agent and method |
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