CN113480990A - Preparation method and application of supercritical carbon dioxide thickening agent - Google Patents
Preparation method and application of supercritical carbon dioxide thickening agent Download PDFInfo
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- CN113480990A CN113480990A CN202110780825.XA CN202110780825A CN113480990A CN 113480990 A CN113480990 A CN 113480990A CN 202110780825 A CN202110780825 A CN 202110780825A CN 113480990 A CN113480990 A CN 113480990A
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a preparation method and application of a supercritical carbon dioxide thickening agent, wherein hydrogen fluoride cyanate ester, an acrylate compound and styrene are used as polymerization monomers and are polymerized under the action of an initiator and an emulsifier, wherein the content of the hydrogen fluoride cyanate ester is 55-65% of the total mole amount of the polymerization monomers, the content of the acrylate compound is 8-12% of the total mole amount of the polymerization monomers, and the content of the styrene compound is 25-30% of the total mole amount of the polymerization monomers. According to the preparation method and the application of the supercritical carbon dioxide thickening agent with the structure, the prepared polymer product has a good thickening effect on the supercritical carbon dioxide, is small in using amount and has good temperature resistance and pressure resistance.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a preparation method and application of a supercritical carbon dioxide thickening agent.
Background
Fracturing has been rapidly developed and widely used as a main means for increasing production and injection of oil and gas reservoirs, and fracturing fluid is an important component of fracturing technology. At present, the most commonly used fracturing fluid at home and abroad is water-based fracturing fluid, and a good yield-increasing effect is achieved. However, the traditional water-based fracturing fluid system has inadaptability to the strong water-sensitive and water-locked low-pressure stratum.
The supercritical carbon dioxide fracturing fluid is a novel fracturing fluid developed in recent years. Supercritical carbon dioxide is a carbon dioxide fluid having a temperature and a pressure higher than their critical values (T ═ 31.1 ℃, P ═ 7.38MPa), and is a third fluid distinguished from gas and liquid in that the gas-liquid interface disappears. The diffusion coefficient and viscosity of the material are close to those of gas, and the density of the material is close to that of liquid. By utilizing the supercritical carbon dioxide for fracturing, the supercritical carbon dioxide has extremely low surface tension and good matrix adsorption strength, and can enter a tiny pore channel after entering a stratum so as to displace oil gas molecules in the tiny pore channel. In addition, a large amount of water resources can be saved, carbon dioxide can be buried, the viscosity of crude oil can be reduced, and the exploitation of the crude oil is facilitated.
At present, the thickening agent used by the supercritical carbon dioxide mainly comprises a silicon-containing polymer which is a kind with ideal cost performance, but contains a large amount of organic solvent, which is not beneficial to storage, transportation and environmental protection.
Disclosure of Invention
The invention aims to provide a preparation method and application of a supercritical carbon dioxide thickening agent.
In order to realize the purpose, the invention provides a preparation method and application of a supercritical carbon dioxide thickener, wherein hydrogen fluoride cyanate, an acrylate compound and styrene are used as polymerization monomers and are polymerized under the action of an initiator and an emulsifier to prepare the thickener;
wherein, the content of the hydrogen fluoride cyanate is 55-65% of the total mole amount of the polymerized monomers, the content of the acrylate compound is 8-12% of the total mole amount of the polymerized monomers, and the content of the styrene is 25-30% of the total mole amount of the polymerized monomers.
Preferably, the hydrocyanic acid fluoride is perfluorotrimethylene diisocyanate, and the isocyanate group isThe perfluoro trimethylene diisocyanate is prepared by degradation reaction of perfluoro glutaryl chloride azide, and the chemical formula of the perfluoro trimethylene diisocyanate is OCN (CF)2)3NCO。
Preferably, the acrylate compound is one of 2- (dimethylamino) ethyl methacrylate, ethylene glycol dimethacrylate, bisphenol a acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, potassium persulfate and ammonium persulfate.
Preferably, the emulsifier is one of sodium dodecyl sulfate, stearate, oleate, span, tween, sucrose stearate and brij.
A preparation method of a supercritical carbon dioxide thickener comprises the following steps:
under the condition of stirring, the components are reacted according to the proportion, and the reaction conditions comprise: the temperature is 80-100 ℃ and the time is 4-8 h.
A supercritical carbon dioxide thickening agent is applied to oil field fracturing fluid.
The invention has the beneficial effects that:
(1) the perfluoro trimethylene diisocyanate contains-NCO group, the cohesive energy of-NCO group is higher, and the surface tension is large, so that the supercritical carbon dioxide thickener has good thickening effect and high thickening speed.
(2) The perfluoro trimethylene diisocyanate contains fluorine atoms in-NCO groups, and the radius of the fluorine atoms is very small, so that the C-F bond is short, the bond energy is high, and the heat resistance, the oxidation resistance, the chemical resistance and other properties of the hydrogen fluoride cyanate are excellent, so that the thickening agent has better temperature resistance and pressure resistance.
(3) The weaker the interaction between chains in or among molecules of the tackifier is, the better the flexibility of the molecular chain is, so that the tackifier is more easily dissolved in CO2Form a homogeneous system, which is beneficial to CO2Dissolving in water.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a test result of a supercritical carbon dioxide thickener prepared according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
The invention provides a preparation method and application of a supercritical carbon dioxide thickener, wherein hydrogen fluoride cyanate ester, an acrylate compound and styrene are used as polymerization monomers and are polymerized under the action of an initiator and an emulsifier to prepare the thickener;
the content of the hydrogen fluoride cyanate is 55-65% of the total mole amount of the polymerization monomers, the content of the acrylate compounds is 8-12% of the total mole amount of the polymerization monomers, and the content of the styrene compounds is 25-30% of the total mole amount of the polymerization monomers.
The hydrocyanic acid fluoride is perfluoro trimethylene diisocyanate, the perfluoro trimethylene diisocyanate is prepared by degradation reaction of perfluoro glutaryl chloride azide, and the chemical formula of the perfluoro trimethylene diisocyanate is OCN (CF)2)3NCO。
The acrylate compound is one of 2- (dimethylamino) ethyl methacrylate, ethylene glycol dimethacrylate, bisphenol A acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate.
The initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, potassium persulfate and ammonium persulfate.
The emulsifier is one of sodium dodecyl sulfate, stearate, oleate, span, tween, sucrose stearate and benezer.
A preparation method of a supercritical carbon dioxide thickener comprises the following steps:
under the condition of stirring, the components are reacted according to the proportion, and the reaction conditions comprise: the temperature is 80-100 ℃ and the time is 4-8 h.
Example 1
Mixing hydrogen fluoride cyanate accounting for 65 percent of the total molar amount of the polymerized monomers, 10 percent of ethylene glycol dimethacrylate and 25 percent of styrene together under the condition of stirring for reaction, adding 45ppm of azobisisobutyronitrile and 250ppm of sodium dodecyl sulfate, heating to 85 ℃, and reacting for 7 hours.
Example 2
Under the condition of stirring, hydrogen fluoride cyanate accounting for 60 percent of the total mole amount of the polymerization monomers, 10 percent of ethylene glycol dimethacrylate and 30 percent of styrene are mixed together for reaction, 45ppm of azobisisobutyronitrile and 250ppm of sodium dodecyl sulfate are added, the temperature is raised to 85 ℃, and the reaction time is 7 hours.
And (3) testing: 5g of each of the products of examples 1 and 2 was dissolved in 20ml of a solvent, and the solution was referred to as a thickener 1 and a thickener 2, respectively, and the thickeners 1 and 2 were added to supercritical carbon dioxide in the amounts shown in Table 1, respectively, and then tested by using a high temperature high pressure viscometer.
Table 1 shows the test conditions and effects of thickening supercritical carbon dioxide with thickener
As can be seen from table 1, the system viscosity of the supercritical carbon dioxide of the thickening agent 1 is higher than that of the supercritical carbon dioxide of the thickening agent 2 under the same amount of the thickening agent, the same pressure and the same temperature.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method and application of a supercritical carbon dioxide thickener are characterized in that hydrogen fluoride cyanate ester, acrylate compound and styrene are used as polymerization monomers and are polymerized under the action of an initiator and an emulsifier to prepare the thickener;
wherein, the content of the hydrogen fluoride cyanate is 55-65% of the total mole amount of the polymerized monomers, the content of the acrylate compound is 8-12% of the total mole amount of the polymerized monomers, and the content of the styrene is 25-30% of the total mole amount of the polymerized monomers.
2. The preparation method and the application of the supercritical carbon dioxide thickener according to claim 1 are characterized in that: the hydrocyanic acid fluoride is perfluorotrimethylene diisocyanate, and the perfluorotrimethylene diisocyanate is prepared by perfluoroglutaryl chloride azide degradation reaction.
3. The preparation method and the application of the supercritical carbon dioxide thickener according to claim 1 are characterized in that: the acrylate compound is one of 2- (dimethylamino) ethyl methacrylate, ethylene glycol dimethacrylate, bisphenol A acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate.
4. The preparation method and the application of the supercritical carbon dioxide thickener according to claim 1 are characterized in that: the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, potassium persulfate and ammonium persulfate.
5. The preparation method and the application of the supercritical carbon dioxide thickener according to claim 1 are characterized in that: the emulsifier is one of sodium dodecyl sulfate, stearate, oleate, span, tween, sucrose stearate and benezer.
6. The method for preparing a supercritical carbon dioxide thickener according to any of claims 1 to 5, comprising the steps of:
under the condition of stirring, the components are reacted according to the proportion, and the reaction conditions comprise: the temperature is 80-100 ℃ and the time is 4-8 h.
7. The supercritical carbon dioxide thickener according to any of claims 1 to 6, wherein: the method is applied to the oil field fracturing fluid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881424A (en) * | 2021-12-07 | 2022-01-04 | 山东德仕化工有限公司 | Composite carbon dioxide fracturing fluid and preparation method thereof |
| CN116751353A (en) * | 2023-05-26 | 2023-09-15 | 陕西延长石油（集团）有限责任公司 | Environment-friendly carbon dioxide thickener and preparation method thereof |
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| CN104388073A (en) * | 2014-11-27 | 2015-03-04 | 中国石油化工股份有限公司 | Supercritical carbon dioxide solid thickening agent as well as preparation method and application thereof |
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2021
- 2021-07-10 CN CN202110780825.XA patent/CN113480990A/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881424A (en) * | 2021-12-07 | 2022-01-04 | 山东德仕化工有限公司 | Composite carbon dioxide fracturing fluid and preparation method thereof |
| CN116751353A (en) * | 2023-05-26 | 2023-09-15 | 陕西延长石油（集团）有限责任公司 | Environment-friendly carbon dioxide thickener and preparation method thereof |
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Application publication date: 20211008 |