CN116948177A - Supercritical carbon dioxide thickener and preparation method thereof - Google Patents
Supercritical carbon dioxide thickener and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 46
- 239000002562 thickening agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BLLPVXQNCYTRTF-UHFFFAOYSA-N 2-ethenyl-2-methylpropane-1,3-diol Chemical compound OCC(C)(CO)C=C BLLPVXQNCYTRTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- VQECZZRUEDMVCU-UHFFFAOYSA-N methoxy-[4-[methoxy(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound CO[Si](C)(C)C1=CC=C([Si](C)(C)OC)C=C1 VQECZZRUEDMVCU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005998 bromoethyl group Chemical group 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 claims description 3
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 claims description 3
- NQVWMPOQWBDSAI-UHFFFAOYSA-N 3-methyloxetan-3-amine Chemical compound CC1(N)COC1 NQVWMPOQWBDSAI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- -1 ether amine Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- AIFBKSGZBRGQJE-UHFFFAOYSA-N 2-(oxetan-3-yl)acetaldehyde Chemical compound O=CCC1COC1 AIFBKSGZBRGQJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000008719 thickening Effects 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 13
- 238000005520 cutting process Methods 0.000 abstract description 10
- 238000005553 drilling Methods 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ROADCYAOHVSOLQ-UHFFFAOYSA-N 3-oxetanone Chemical compound O=C1COC1 ROADCYAOHVSOLQ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
Classifications
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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
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to the field of innocent treatment of oil-based drilling cuttings, in particular to a supercritical carbon dioxide thickener and a preparation method thereof, wherein the preparation raw materials are as follows: 1, 4-bis (methoxydimethylsilyl) benzene, 2-vinyl-2-methyl-1, 3-propanediol, alkenoic acids, 2- (bromoethyl) -2-methyl acrylate and etheramines. The supercritical carbon dioxide thickener provided by the invention has good solubility in supercritical carbon dioxide, excellent thickening performance, capability of expanding the viscosity of the supercritical carbon dioxide to 196 times, 99.94% of average extraction rate of oil phase in oil-based drilling cuttings, low cost, easily available raw materials and capability of realizing large-scale application.
Description
Technical Field
The invention relates to the field of innocent treatment of oil-based drilling cuttings, in particular to a supercritical carbon dioxide thickener and a preparation method thereof.
Background
Along with development of shale gas exploitation in China, oil-based drilling cuttings generated by using oil-based drilling fluid in the drilling process are increased, the oil-based drilling cuttings belong to dangerous wastes, the dangerous wastes are subjected to innocent treatment, and at present, most of the oil-based drilling cuttings are treated by using a pyrolysis mode, but harmful substances are generated in the treatment method, and the treated drilling cuttings are difficult to reach the local hazardous waste treatment standard. Supercritical carbon dioxide extraction is an efficient and environment-friendly separation technology, oil in rock debris can be safely, cleanly and efficiently extracted by using the supercritical carbon dioxide extraction technology, and the extracted oil phase can be recycled. However, supercritical carbon dioxide has low viscosity, unstable extraction effect and easy dissipation in the extraction process. Therefore, it is necessary to solve the problem of low viscosity of carbon dioxide, and research on supercritical carbon dioxide thickeners is performed.
Current carbon dioxide thickeners can be broadly divided into three categories of elements based on the functional groups: (1) The fluorine-containing thickener has good solubility of fluorine-containing compounds in supercritical carbon dioxide and good thickening effect, but the fluorine-containing substances are expensive and have great damage to the environment, so that the wide application of the fluorine-containing thickener is severely limited; (2) Silicone thickeners, which have poor solubility in supercritical carbon dioxide, often require the use of a co-solvent, which is expensive. (3) Hydrocarbon and its derivative thickeners are relatively low cost, but hydrocarbon polymers are not ideal in thickening effect. For example, CN108003349B discloses a preparation method of a supercritical carbon dioxide thickener, and the final product is a polymer containing siloxane, phenyl and amide groups, and the polymer has a certain thickening effect, but the thickening effect is still not obvious. Therefore, the development of a supercritical carbon dioxide thickener with better solubility and thickening property is a problem to be solved urgently.
Disclosure of Invention
The invention provides a supercritical carbon dioxide thickener and a preparation method thereof, which can effectively solve the problems.
The first aspect of the invention provides a method for preparing a supercritical carbon dioxide thickener, comprising the following steps:
(1) Adding 1, 4-bis (methoxydimethylsilyl) benzene and 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) into tetrahydrofuran, stirring and heating under the atmosphere of nitrogen, reacting at 160-200 ℃ for 2-4 hours, fractionating after the reaction is completed, and purifying to obtain a siloxane-containing intermediate; the molar ratio of the 2-vinyl-2-methyl-1, 3-propanediol to the 1, 4-bis (methoxydimethylsilyl) benzene is (1.6-2.5): 1
(2) Adding a siloxane-containing intermediate of the product obtained in the step (1) into a reactor, then adding an initiator, then adding acrylic acid, starting stirring and heating, heating to 70-90 ℃, reacting for 2-4 hours, adding water for washing after the reaction is finished, and purifying to obtain a product intermediate A;
(3) Adding triethylamine into a reactor containing a product intermediate A, then adding an acetone solution of 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5), stirring at 20-30 ℃ to react for 1-2 hours, and carrying out reduced pressure distillation and purification after the reaction is completed to obtain a product intermediate B;
(4) Adding ethanol, then adding etheramine, then adding a product intermediate B, stirring at 20-30 ℃ to react for 4-6 hours, distilling under reduced pressure, adding water for washing, and drying to obtain the supercritical carbon dioxide thickener.
The initiator in the step (2) is azodiisobutyronitrile, and the initiator dosage is 1-5% of the reactant mass; the olefinic acids are: one of 4-pentene-1, 2-tricarboxylic acid (CAS number: 1824311-13-8), 2-methyl-2-allyl-1, 4-succinic acid (CAS number: 113661-33-9), 2-ethyl-2-allyl-1, 3-malonic acid (CAS number: 4355-03-7).
The ether amine in the step (4) is one of 2, 2-dimethoxyethylamine, 3-amino-3-methyl oxetane, 3-oxetane and aminoacetaldehyde diethyl acetal.
In a second aspect, the present invention provides a supercritical carbon dioxide thickener prepared by the above preparation method.
The technical scheme of the embodiment of the invention has at least the following advantages and beneficial effects:
the novel supercritical carbon dioxide thickener provided by the invention has the advantages that the ester group improves the solubility of the novel supercritical carbon dioxide thickener in carbon dioxide, the siloxane has good chain flexibility, the novel supercritical carbon dioxide thickener has good thickening effect on supercritical carbon dioxide, and the thickening effect is improved by introducing phenyl; the invention has excellent thickening effect on supercritical carbon dioxide, has low price and easily obtained raw materials, and can realize large-scale application.
Drawings
FIG. 1 shows one of the structural formulae of the product of the present invention.
FIG. 2 shows one of the structural formulae of the product of the present invention.
FIG. 3 shows one of the structural formulae of the product of the present invention.
Detailed Description
The technical scheme of the invention will be clearly and completely described in the following in connection with the embodiments of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without undue burden are within the scope of the invention
The embodiment of the invention is as follows:
example 1
(1) 25.65g of 1, 4-bis (methoxydimethylsilyl) benzene and 16.84g of 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) are added into a three-necked flask containing 50mL of toluene, nitrogen is introduced into the three-necked flask, the mixture is stirred and heated to 180 ℃ under the atmosphere of nitrogen, the mixture is stirred and reacted for 2 hours, and the mixture is fractionated and purified to obtain an intermediate containing siloxane;
(2) Adding 25g of the intermediate containing siloxane obtained in the step (1) into a three-necked flask, then adding 1g of azodiisobutyronitrile, then adding 40.44g of 4-pentene-1, 2-tricarboxylic acid (CAS number: 1824311-13-8), placing the mixture in a water bath kettle, stirring and heating to 80 ℃, reacting for 3 hours, washing with water after the reaction is finished, and purifying to obtain a product intermediate A;
(3) 45g of the product intermediate A obtained in the step (2) is added into a three-necked flask containing 50mL of triethylamine, 100.21g of an acetone solution containing 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5) is added into the three-necked flask, the mixture is stirred at 25 ℃ to react for 1 hour, and after the reaction is completed, reduced pressure distillation is carried out, and the product intermediate B is obtained by purification;
(4) 21.03g of 2, 2-dimethoxyethylamine is added into a three-necked flask containing 50mL of ethanol, 115g of the product intermediate B obtained in the step (3) is added into the three-necked flask, the mixture is stirred at 25 ℃ to react for 5 hours, and after the reaction is finished, the mixture is distilled under reduced pressure, washed by adding water and dried to obtain the supercritical carbon dioxide thickener.
Example 2
(1) 25.65g of 1, 4-bis (methoxydimethylsilyl) benzene and 16.84g of 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) are added into a three-necked flask containing 50mL of toluene, nitrogen is introduced into the three-necked flask, the mixture is stirred and heated to 180 ℃ under the atmosphere of nitrogen, the mixture is stirred and reacted for 2 hours, and the mixture is fractionated and purified to obtain an intermediate containing siloxane;
(2) Adding 25g of the intermediate containing siloxane obtained in the step (1) into a three-necked flask, then adding 1g of azodiisobutyronitrile, then adding 34.44g of 2-methyl-2-allyl-1, 4-succinic acid (CAS number: 113661-33-9), placing the mixture into a water bath kettle, stirring and heating to 80 ℃, reacting for 3 hours, adding water for washing after the reaction is finished, and purifying to obtain a product intermediate A;
(3) Adding 40g of the product intermediate A obtained in the step (2) into a three-necked flask containing 50mL of triethylamine, adding 100.21g of an acetone solution containing 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5) into the three-necked flask, stirring the mixture at 25 ℃ to react for 1 hour, and distilling the mixture under reduced pressure after the reaction is finished to obtain a product intermediate B;
(4) 26.64g of aminoacetaldehyde diethyl acetal is added into a three-necked flask containing 50mL of ethanol, 98g of the product intermediate B obtained in the step (3) is added into the three-necked flask, the mixture is stirred at 25 ℃ to react for 5 hours, and after the reaction is finished, the mixture is distilled under reduced pressure, washed by adding water and dried to obtain the supercritical carbon dioxide thickener.
Example 3
(1) 25.65g of 1, 4-bis (methoxydimethylsilyl) benzene and 16.84g of 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) are added into a three-necked flask containing 50mL of toluene, nitrogen is introduced into the three-necked flask, the mixture is stirred and heated to 180 ℃ under the atmosphere of nitrogen, the mixture is stirred and reacted for 2 hours, and the mixture is fractionated and purified to obtain an intermediate containing siloxane;
(2) Adding 25g of the intermediate containing siloxane obtained in the step (1) into a three-necked flask, then adding 1g of azodiisobutyronitrile, then adding 34.44g of 2-methyl-2-allyl-1, 4-succinic acid (CAS number: 113661-33-9), placing the mixture into a water bath kettle, stirring and heating to 80 ℃, reacting for 3 hours, adding water for washing after the reaction is finished, and purifying to obtain a product intermediate A;
(3) Adding 40g of the product intermediate A obtained in the step (2) into a three-necked flask containing 50mL of triethylamine, adding 100.21g of an acetone solution containing 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5) into the three-necked flask, stirring the mixture at 25 ℃ to react for 1 hour, and distilling the mixture under reduced pressure after the reaction is finished to obtain a product intermediate B;
(4) 17.43g of 3-amino-3-methyl oxetane is added into a three-necked flask containing 50mL of ethanol, 98g of the product intermediate B obtained in the step (3) is added into the three-necked flask, the mixture is stirred at 25 ℃ to react for 5 hours, and after the reaction is finished, the mixture is distilled under reduced pressure, washed by adding water and dried to obtain the supercritical carbon dioxide thickener.
Example 4
(1) 25.65g of 1, 4-bis (methoxydimethylsilyl) benzene and 16.84g of 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) are added into a three-necked flask containing 50mL of toluene, nitrogen is introduced into the three-necked flask, the mixture is stirred and heated to 180 ℃ under the atmosphere of nitrogen, the mixture is stirred and reacted for 2 hours, and the mixture is fractionated and purified to obtain an intermediate containing siloxane;
(2) Adding 25g of the intermediate containing siloxane obtained in the step (1) into a three-necked flask, then adding 1g of azodiisobutyronitrile, then adding 34.44g of 2-ethyl-2-allyl-1, 3-malonic acid (CAS number: 4355-03-7), placing the mixture into a water bath kettle, stirring and heating to 80 ℃, reacting for 3 hours, adding water for washing after the reaction is finished, and purifying to obtain a product intermediate A;
(3) Adding 40g of the product intermediate A obtained in the step (2) into a three-necked flask containing 50mL of triethylamine, adding 100.21g of an acetone solution containing 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5) into the three-necked flask, stirring the mixture at 25 ℃ to react for 1 hour, and distilling the mixture under reduced pressure after the reaction is finished to obtain a product intermediate B;
(4) 14.62g of 3-oxetanone is added into a three-necked flask containing 50mL of ethanol, 98g of the product intermediate B obtained in the step (3) is added into the three-necked flask, the mixture is stirred at 25 ℃ to react for 5 hours, and after the reaction is finished, the mixture is distilled under reduced pressure, washed by adding water and dried to obtain the supercritical carbon dioxide thickener.
Comparative example 1
Comparative example 1 is a polydimethylsiloxane purchased from the scientific company of belvedere.
The final products of examples 1-4 and comparative example 1 were added to supercritical carbon dioxide in a mass to volume ratio of 1%, 2%, 3%, 4% (e.g., 1g, 2g, 3g, 4g of thickener per 100mL of supercritical carbon dioxide, respectively), and viscosity measurements were performed at 35 ℃ and 10MPa using a visclolabpvt viscometer, with viscosity ratio (as compared to pure supercritical carbon dioxide) data shown in table 1.
As shown in Table 1, the invention has obvious thickening effect, and can achieve good thickening effect when being added with 3 percent of mass and volume ratio, and can reach 196 times compared with pure supercritical carbon dioxide. Under the same test conditions, examples 1-4 are significantly higher than the viscosity ratio of the comparative examples, indicating that the present invention has good adhesion enhancing capability to supercritical carbon dioxide. Under the same test conditions, example 1 has a higher viscosity ratio than other examples, demonstrating that properly increasing the solubilizing group of the thickener is beneficial to improving the thickening effect. As the mass-volume ratio of the thickener to the supercritical carbon dioxide is increased from 1% to 3%, the thickening effect is remarkably improved, and the thickening effect is not obviously changed when the mass-volume ratio is increased to 4%. Example 1 is the best embodiment of the invention.
TABLE 1 evaluation results of thickening Effect
| Numbering device | Average viscosity ratio (times) |
| 1% example 1 | 169 |
| 2% example 1 | 181 |
| 3% example 1 | 196 |
| 4% example 1 | 194 |
| 1% example 2 | 153 |
| 2% example 2 | 168 |
| 3% example 2 | 186 |
| 4% example 2 | 187 |
| 1% example 3 | 153 |
| 2% example 3 | 170 |
| 3% example 3 | 183 |
| 4% example 3 | 189 |
| 1% example 4 | 151 |
| 2% example 4 | 167 |
| 3% example 4 | 185 |
| 4% example 4 | 184 |
| 1% comparative example 1 | 27 |
| 2% comparative example 1 | 35 |
| 3% comparative example 1 | 41 |
| 4% comparative example 1 | 44 |
The final products of examples 1-4 and comparative example 1 were mixed with supercritical carbon dioxide in amounts of 1%, 2%, 3% and 4% by mass/volume, respectively (e.g., 1g, 2g, 3g and 4g of thickener were added to each 100mL of supercritical carbon dioxide), and each mass concentration of the mixture was subjected to 3 supercritical carbon dioxide extraction oil-based cuttings experiments in a reaction vessel at 35 ℃ and 10MPa, respectively, and the average extraction rate data are shown in table 2.
As shown in Table 2, the invention has obvious extraction effect, and the average extraction rate can reach 99.94%. Examples 1-4 were significantly more effective than the comparative examples under the same test conditions, indicating that the present invention has good extraction capacity for the oil phase in oil-based drill cuttings. The extraction effect can be very good when the mass volume ratio is 3%. With the mass-volume ratio of the thickener to the supercritical carbon dioxide being increased from 1% to 3%, the extraction rate is remarkably increased, and the change of the extraction rate is not obvious when the mass-volume ratio is increased to 4%. The improvement of the extraction effect also reflects the remarkable thickening effect of the invention. Example 1 is the best embodiment of the invention.
TABLE 2 evaluation results of extraction effect
In conclusion, the invention has obvious thickening effect, low consumption of carbon dioxide in a thickener, 196 times of viscosity, 99.94% of average extraction rate of oil phase in oil-based drilling cuttings, and reaching local hazardous waste treatment standard, and compared with a pyrolysis method, the invention has obvious technical advantages, safety, high efficiency, environmental protection, low cost and realization of large-scale application.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, and any simple modification, equivalent variations and adaptations of the above embodiments according to the technical principles of the present invention without departing from the technical scope of the present invention will still fall within the scope of the technical scope of the present invention.
Claims (5)
1. A supercritical carbon dioxide thickener and a preparation method thereof are characterized in that the raw materials of the material are mainly: 1, 4-bis (methoxydimethylsilyl) benzene, 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6), alkenoic acid, methyl 2- (bromoethyl) -2-acrylate (CAS number: 4224-69-5), etheramine, the preparation comprising the steps of:
(1) Taking 6-15 mol parts of 1, 4-bis (methoxydimethylsilyl) benzene and 12-30 mol parts of 2-vinyl-2-methyl-1, 3-propanediol (CAS number: 99115-97-6) to be added into tetrahydrofuran, stirring and heating under the atmosphere of nitrogen, reacting for 2-4 hours at 160-200 ℃, after the reaction is completed, fractionating and purifying to obtain an intermediate containing siloxane; the molar ratio of the 2-vinyl-2-methyl-1, 3-propanediol to the 1, 4-bis (methoxydimethylsilyl) benzene is (1.6-2.5): 1, a step of;
(2) Adding the intermediate containing siloxane of the product obtained in the step (1) into a reactor, then adding an initiator, adding 12-30 mol parts of olefinic acid, starting stirring and heating, heating to 70-90 ℃ to react for 2-4 hours, adding water for washing after the reaction is finished, and purifying to obtain a product intermediate A;
(3) Adding triethylamine into a reactor containing a product intermediate A, then adding 36-90 mol parts of 2- (bromoethyl) -2-methyl acrylate (CAS number: 4224-69-5) into the mixture, stirring the mixture at 20-30 ℃ to react for 1-2 hours, and carrying out reduced pressure distillation and purification after the reaction is completed to obtain a product intermediate B;
(4) Adding ethanol into a reaction vessel, adding 12-30 mol parts of etheramine, adding a product intermediate B into the reaction vessel, stirring at 20-30 ℃ to react for 4-6 hours, distilling under reduced pressure, adding water for washing, and drying to obtain the supercritical carbon dioxide thickener.
2. The method for preparing a carbon dioxide thickener according to claim 1, wherein the initiator in the step (2) is azobisisobutyronitrile, and the amount of the initiator is 1-5% of the mass of the reactant.
3. The method for producing a carbon dioxide thickener according to claim 1, wherein the olefinic acids in the step (2) are: one of 4-pentene-1, 2-tricarboxylic acid (CAS number: 1824311-13-8), 2-methyl-2-allyl-1, 4-succinic acid (CAS number: 113661-33-9), 2-ethyl-2-allyl-1, 3-malonic acid (CAS number: 4355-03-7).
4. The method for producing a carbon dioxide thickener according to claim 1, wherein the ether amine in the step (4) is one of 2, 2-dimethoxyethylamine, 3-amino-3-methyl oxetane, 3-oxetane, and aminoacetaldehyde diethyl acetal.
5. A supercritical carbon dioxide thickener prepared by the method for preparing a carbon dioxide thickener according to any of claims 1 to 4.
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