CN111268687B - Organic clay composition and preparation method thereof - Google Patents
Organic clay composition and preparation method thereof Download PDFInfo
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- CN111268687B CN111268687B CN202010149948.9A CN202010149948A CN111268687B CN 111268687 B CN111268687 B CN 111268687B CN 202010149948 A CN202010149948 A CN 202010149948A CN 111268687 B CN111268687 B CN 111268687B
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- stirring
- quaternary ammonium
- ammonium salt
- constant temperature
- clay
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- 239000004927 clay Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000725 suspension Substances 0.000 claims abstract description 52
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004113 Sepiolite Substances 0.000 claims abstract description 26
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 26
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 26
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 23
- -1 alkyl quaternary ammonium salt Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 11
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 238000005553 drilling Methods 0.000 abstract description 10
- 230000008719 thickening Effects 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 17
- 239000002689 soil Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229910000278 bentonite Inorganic materials 0.000 description 9
- 239000000440 bentonite Substances 0.000 description 9
- 229940092782 bentonite Drugs 0.000 description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 8
- 239000003607 modifier Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 5
- 229910000280 sodium bentonite Inorganic materials 0.000 description 5
- 229940080314 sodium bentonite Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229940049918 linoleate Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 2
- 229940066675 ricinoleate Drugs 0.000 description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 2
- DJIOGHZNVKFYHH-UHFFFAOYSA-N 2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=N1 DJIOGHZNVKFYHH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229950004959 sorbitan oleate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to an organic clay composition which can be used as a thickening rheological aid and can be used in the fields of paint, printing ink, oil field drilling and the like. An organoclay composition comprises montmorillonite, sepiolite and long chain alkyl quaternary ammonium salt. The organic clay composition mainly comprises montmorillonite, sepiolite and long-chain alkyl quaternary ammonium salt, and also comprises a small amount of organic auxiliary agent; and is prepared by a specific process. The organic clay composition obtained by the modification of the process has the advantages of good dispersibility, suspension property and thickening property, high rheological property and capability of effectively promoting the application in a low-polarity system.
Description
Technical Field
The invention relates to an organic clay composition and a preparation method thereof, wherein the organic clay composition can be used as a thickening rheological aid and can be used in the fields of paint, printing ink, oil field drilling and the like.
Background
Clay is an important mineral raw material, widely existing in nature, and generally formed by weathering aluminosilicate minerals on the earth's surface. Its main components are composed of various hydrated silicates and a certain amount of alumina, alkali metal oxide and alkaline earth metal oxide, and it contains quartz, feldspar, mica and impurities of sulfate, sulfide and carbonate. Clay minerals are generally fine particles, often in the colloidal size range, crystalline or amorphous, mostly lamellar, and a few tubular or rod-shaped. The clay minerals are most widely applied to bentonite, sepiolite, attapulgite, kaolin and the like. The microstructure of bentonite is mainly lamellar, and the microstructure of sepiolite and attapulgite is mainly rod-shaped or fibrous. Wherein the mineral with high cation exchange capacity is bentonite or sepiolite.
Organoclays generally refer to organically modified clays. The surface of the clay particles changes from hydrophilic to hydrophobic. Can be widely applied to the fine chemical engineering fields of petroleum drilling fluid, paint, printing ink, polymer nano composite material and the like, and can be used as thickening rheological additive and functional additive.
The invention patent document with the application number of 201810060193.8 discloses a composite organic clay for an oil-based drilling fluid and a compounding method thereof. The preparation of the organic montmorillonite and the fibrous organic clay and the compounding of the organic montmorillonite and the fibrous organic clay according to a certain proportion to prepare the oil-based drilling fluid are provided. The organic montmorillonite and the fibrous organic clay are prepared respectively and then are compounded and used in the formula of the oil-based drilling fluid to improve the temperature resistance.
Patent No. 201310034512.5, which is an invention patent document, discloses a preparation method of modified organic bentonite. Sodium bentonite is added into water and stirred to prepare sodium bentonite suspension; dissolving cetyl trimethyl ammonium bromide in water at room temperature, adding sorbitan oleate, and stirring to obtain emulsion; and then mixing and oscillating the emulsion and the sodium bentonite suspension, and then centrifuging, washing, drying and crushing to obtain the modified organic bentonite which is used as the white oil-based drilling fluid additive.
The invention patent document with the patent number of 201710265478.0 discloses a preparation method of novel organic modified sepiolite and application of the organic modified sepiolite. The sepiolite is purified firstly, and then modified by a cation modifier and an anion modifier to obtain the organic modified sepiolite, wherein the cation modifier is not quaternary ammonium salt with 14-18 carbons, and the anion modifier is sodium dodecyl sulfate or sodium hexadecyl sulfate. The organic modified sepiolite has good dispersibility, thixotropy and high viscosity, and meets the use requirements of oil-based drilling.
The invention patent document of application No. 201610782449.7 discloses a preparation method of organobentonite. The method comprises the steps of taking calcium bentonite as a raw material, adding sodium carbonate for sodium treatment to obtain sodium bentonite slurry, then adding polyacrylamide for reaction, performing filter pressing, then adding dibutyl phthalate (emulsifier) for modification, transferring the mixture into a mixing mill, and mixing the mixture with dimethyl octadecyl benzyl ammonium chloride to obtain the organic bentonite.
Patent No. 201110235817.3 discloses a preparation method of high-performance organic bentonite. The sodium bentonite is used as a raw material, and two types of modifiers are adopted for modification, wherein one type of modifiers is quaternary ammonium salt (one of hexadecyl trimethyl ammonium chloride, hexadecyl pyridine, octadecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride), and the other type of modifiers is an intercalating agent (one of caprolactam, fatty alcohol polyoxyethylene ether AEO and octadecyl polyoxyethylene ether). The prepared organic bentonite is beneficial to improving the rheological property and the rock carrying capacity of the drilling fluid.
In conclusion, the clay minerals for modifying the organic clay mainly comprise bentonite, sepiolite and fibrous clay, and the modifying agent mainly comprises quaternary ammonium salts with different carbon chain lengths. In order to improve the suspension stability of the organoclay in an oily system, a nonionic or anionic surfactant is added on the basis of quaternary ammonium salt modification, so that the purpose of synergy is achieved.
The organic clay has good and bad application performance in the fields of paint, printing ink, oil field drilling and the like, and is mainly represented by thickening, suspending and thixotropic properties in corresponding fields. The use of a single type of clay to make organoclays tends to exhibit inadequate thickening or suspending properties during use. The invention aims to select proper clay for compounding and prepare an organic clay product with high thickening performance through the optimization of a modification auxiliary agent.
Disclosure of Invention
The present invention is to solve the above problems, and thus provides an organoclay composition. The organoclay compositions of the present invention have the advantage of high rheology.
The technical scheme for solving the problems is as follows:
an organoclay composition mainly comprises montmorillonite, sepiolite and long chain alkyl quaternary ammonium salt; the organic clay composition comprises the following components in parts by mass:
montmorillonite: 50 to 70 percent of the total weight of the mixture,
sepiolite: 10 to 30 percent of the total weight of the composition,
long-chain alkyl quaternary ammonium salts: 30 to 50 percent of the total weight of the composition,
auxiliary agent: 1.1 to 15.
Preferably, the montmorillonite is selected from one or two of sodium montmorillonite and artificial sodium montmorillonite; the auxiliary agent comprises an auxiliary agent A and an auxiliary agent B, wherein the auxiliary agent A is selected from one or more of low molecular weight polyacrylate (molecular weight is 500-5000), low molecular weight polyacrylate (molecular weight is 500-5000) and hydroxyl carboxylate; the addition amount of the additive A is 0.1-5% of the mass of the clay powder; the auxiliary agent B is selected from one or more of oleamide, fatty acid amide, lactic acid fatty acid amide, stearic acid amide, oleate, linoleate and ricinoleate; the dosage of the assistant B is 1-10% of the mass of the clay powder.
It is another object of the present invention to provide a process for preparing the above clay composition.
A method of making an organoclay composition comprising the steps of:
1) Dispersing clay powder in water, stirring, centrifuging and purifying to form suspension with the concentration of 2-6 wt%;
2) Adding a pH regulator into the suspension, adjusting the pH of the slurry to be between 5 and 9, and stirring for 0.5 to 1 hour at the constant temperature of between 40 and 80 ℃;
3) Adding the assistant A, and stirring at the constant temperature of 40-80 ℃ for 0.5-1 hour;
4) Adding long-chain alkyl quaternary ammonium salt for modification, and stirring at the constant temperature of 40-80 ℃ for 1-10 hours;
5) Adding the assistant B, and stirring at the constant temperature of 40-80 ℃ for 0.5-1 hour;
6) Adding a pH regulator, adjusting the pH of the slurry to be between 8 and 10, and stirring for 0.5 to 1 hour at the constant temperature of between 40 and 80 ℃;
7) Filtering, washing, drying and crushing to obtain a product;
the assistant A is selected from one or more of low molecular weight polyacrylate (molecular weight is 500-5000), low molecular weight polyacrylate (molecular weight is 500-5000) and hydroxyl carboxylate; the addition amount of the additive A is 0.1-5% of the mass of the clay powder;
the auxiliary agent B is selected from one or more of oleic acid amide, fatty acid amide, lactic acid fatty acid amide, stearic acid amide, oleate, linoleate and ricinoleate; the dosage of the assistant B is 1 to 10 percent of the mass of the clay powder.
Preferably, the addition amount of the aid A is 0.2 to 3% by mass of the clay powder.
Preferably, the addition amount of the auxiliary B is 2 to 7% by mass of the clay powder.
Preferably, the clay powder of step 1) comprises montmorillonite and sepiolite, and the montmorillonite is selected from one or two of sodium-based montmorillonite and artificial sodium montmorillonite.
Preferably, the pH regulator in step 2) and step 6) is one or more selected from sulfuric acid, hydrochloric acid, triethanolamine and sodium hydroxide.
Preferably, the long-chain alkyl quaternary ammonium salt in the step 4) has a structural formula:
wherein M is chloride or bromide;
wherein R1 is CH 3 （CH 2 ） n -,n=11～21；
Wherein R2 is CH 3 -or CH 3 （CH 2 ） n -,n=11～21；
Wherein R3 and R4 are CH 3 -。
Preferably, the long-chain alkyl quaternary ammonium salt in the step 4) consists of two components, namely quaternary ammonium salt A and quaternary ammonium salt B, wherein R2 of the quaternary ammonium salt A is CH 3 （CH 2 ） n -n =11 to 21; r2 of quaternary ammonium salt B is CH 3 -; wherein the dosage of the quaternary ammonium salt A is 15-50% of the mass of the clay, and the dosage of the quaternary ammonium salt B is 10-40% of the mass of the clay.
The purpose of the step 4) is to perform intercalation modification on the viscosity material, wherein the quaternary ammonium salt A has an obvious effect of improving the interlayer spacing of the montmorillonite, and the quaternary ammonium salt B has a complementary intercalation effect on the clay. The two quaternary ammonium salts are used simultaneously to prepare a sample with good dispersion, suspension and thickening performances.
The step 5) of the invention aims to insert nonionic organic molecules into the clay layers by the adsorption principle to achieve the emulsification and dispersion effects, and the step has obvious promotion effect on the application of the product in a low-polarity system.
Preferably, the water content of the product obtained after drying and crushing in the step 7) is less than or equal to 5 percent, and the fineness of the dry powder is less than or equal to 200 meshes.
In conclusion, the invention has the following beneficial effects:
the organic clay composition mainly comprises montmorillonite, sepiolite and long-chain alkyl quaternary ammonium salt, and also comprises a small amount of organic auxiliary agent; and is prepared by a specific process. The organoclay composition modified by the process disclosed by the invention has the advantages of good dispersibility, good suspension property and good thickening property, and high rheological property, and can be effectively promoted to be applied to a low-polarity system.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples. The examples are only for explaining the present invention and do not constitute a limitation to the scope of protection of the present invention.
Example 1 was carried out:
weighing 1000g of sodium-based montmorillonite powder, adding 20kg of water, fully stirring and dispersing, and performing centrifugal purification to obtain a purified sodium-based montmorillonite suspension, wherein the solid content of the suspension is tested to be 30g/L. Taking 5L of purified sodium-based montmorillonite suspension, placing the suspension in a reactor, heating to 70 ℃, and keeping stirring at constant temperature; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, adding 3g (2% soil) of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at a constant temperature of 70 ℃; adding 70g (47% soil) of dioctadecyl dimethyl ammonium chloride and 40g (27% soil) of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 7.5g (5% soil) of oleamide, and stirring for 1h at the constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-1.
Example 2 was carried out:
weighing 500g of sepiolite powder, adding 10kg of water, fully stirring and dispersing, and carrying out centrifugal purification to obtain the purified sepiolite suspension. The solid content of the test suspension is 20g/L. Taking 5L of purified sepiolite suspension, heating to 70 ℃, and keeping constant temperature and stirring; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at a constant temperature of 70 ℃; adding 47g of dioctadecyl dimethyl ammonium chloride and 27g of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 5g of oleamide, and stirring for 1h at the constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-2.
Example 3 of implementation:
weighing 4L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 1L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 28g/L. Heating the mixed clay suspension to 70 ℃, and keeping stirring at constant temperature; adding dilute sulfuric acid, regulating the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.8g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at the constant temperature of 70 ℃; adding 66g of dioctadecyl dimethyl ammonium chloride and 37.8g of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 7g of oleamide, stirring for 1h at constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting the pH value of the slurry to 8-9, stirring at the constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying and crushing to obtain a sample, wherein the label is FH-3.
Example 4 of implementation:
weighing 3L of the purified sodium-based montmorillonite suspension in the embodiment 1, weighing 2L of the purified sepiolite suspension in the embodiment 2, fully stirring and mixing to obtain a mixed clay suspension, and testing the solid content of the suspension to be 26g/L. Heating the mixed clay suspension to 70 ℃, and keeping stirring at constant temperature; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.6g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at a constant temperature of 70 ℃; adding 61g of dioctadecyl dimethyl ammonium chloride and 35g of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 6.5g of oleamide, and stirring for 1h at the constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-4.
Example 5 was carried out:
weighing 2.5L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 2.5L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 25g/L. Heating the mixed clay suspension to 70 ℃, and keeping constant-temperature stirring; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.5g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at the constant temperature of 70 ℃; adding 59g of dioctadecyl dimethyl ammonium chloride and 34g of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 6.2g of oleamide, and stirring for 1h at the constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-5.
Example 6 of implementation:
weighing 4L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 1L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 28g/L. Heating the mixed clay suspension to 70 ℃, and keeping constant-temperature stirring; adding dilute sulfuric acid, regulating the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.8g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at the constant temperature of 70 ℃; adding 56g (40% soil) of dioctadecyl dimethyl ammonium chloride and 28g (20% soil) of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 7g of oleamide, stirring for 1h at constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-6.
Example 7 was carried out:
weighing 4L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 1L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 28g/L. Heating the mixed clay suspension to 70 ℃, and keeping constant-temperature stirring; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.8g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at the constant temperature of 70 ℃; adding 70g (50% soil) of dioctadecyl dimethyl ammonium chloride and 42g (30% soil) of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 7g of oleamide, stirring for 1h at constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting the pH value of the slurry to 8-9, stirring at the constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying and crushing to obtain a sample, wherein the label is FH-7.
Example 8 was carried out:
weighing 4L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 1L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 28g/L. Heating the mixed clay suspension to 70 ℃, and keeping constant-temperature stirring; adding dilute sulfuric acid, adjusting the pH value of the slurry to 7-8, stirring for 30 minutes, and stirring for 1 hour at the constant temperature of 70 ℃; adding 70g (50% soil) of dioctadecyl dimethyl ammonium chloride and 42g (30% soil) of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding 7g of oleamide, stirring for 1h at constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting pH of the slurry to 8-9, stirring at constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying, and crushing to obtain a sample, wherein the label is FH-8.
Example 9 was carried out:
weighing 4L of the purified sodium-based montmorillonite suspension in the embodiment example 1, weighing 1L of the purified sepiolite suspension in the embodiment example 2, fully stirring and mixing to obtain a mixed clay suspension, wherein the solid content of the test suspension is 28g/L. Heating the mixed clay suspension to 70 ℃, and keeping stirring at constant temperature; adding dilute sulfuric acid, regulating the pH value of the slurry to 7-8, stirring for 30 minutes, adding 2.8g of low-molecular-weight sodium polyacrylate, and stirring for 1 hour at the constant temperature of 70 ℃; adding 70g (50% soil) of dioctadecyl dimethyl ammonium chloride and 42g (30% soil) of octadecyl trimethyl ammonium chloride, and stirring for 2 hours at the constant temperature of 70 ℃; adding sodium hydroxide solution, adjusting the pH value of the slurry to 8-9, stirring at the constant temperature of 70 ℃ for 30 minutes, cooling to room temperature, filtering, washing, drying and crushing to obtain a sample, wherein the label is FH-9.
The rheological viscosity of the sample in the example is measured by dispersing the sample in white oil, and the measuring method is as follows: weighing 10g of organic clay sample, dispersing in 90g of white oil, stirring and dispersing at 2000rpm for 10min, keeping the temperature constant at about 30 ℃ during stirring, preparing gel, and placing the gel in a rotational viscosity agent for viscosity test. The test results are shown in table 1.
As can be seen from the table, the samples prepared according to the inventive protocol have a high thickening performance in solvents.
Table 1: sample rheological viscosity test data
Claims (7)
1. A method of preparing an organoclay composition comprising the steps of:
1) Dispersing clay powder in water, stirring, centrifuging and purifying to form suspension with the concentration of 2-6 wt%;
2) Adding a pH regulator into the suspension, adjusting the pH of the slurry to be between 5 and 9, and stirring for 0.5 to 1 hour at the constant temperature of between 40 and 80 ℃;
3) Adding the assistant A, and stirring at the constant temperature of 40-80 ℃ for 0.5-1 hour;
4) Adding long-chain alkyl quaternary ammonium salt for modification, and stirring at the constant temperature of 40-80 ℃ for 1-10 hours;
5) Adding the assistant B, and stirring at the constant temperature of 40-80 ℃ for 0.5-1 hour;
6) Adding a pH regulator, adjusting the pH of the slurry to be between 8 and 10, and stirring for 0.5 to 1 hour at the constant temperature of between 40 and 80 ℃;
7) Filtering, washing, drying and crushing to obtain a product;
the assistant A is selected from one or more of low molecular weight polyacrylate, low molecular weight polyacrylate and hydroxyl carboxylate; the addition amount of the additive A is 0.1-5% of the mass of the clay powder;
the auxiliary agent B is selected from one or more of oleamide, fatty acid amide, lactic acid fatty acid amide and stearic acid amide; the dosage of the assistant B is 1 to 10 percent of the mass of the clay powder;
the pH regulator in the steps 2) and 6) is one or more selected from sulfuric acid, hydrochloric acid, triethanolamine and sodium hydroxide.
2. The process of claim 1 for preparing an organoclay composition, wherein: the addition amount of the additive A is 0.2-3% of the mass of the clay powder.
3. The method of preparing an organoclay composition according to claim 1, wherein: the addition amount of the auxiliary agent B is 2-7% of the mass of the clay powder.
4. The process of claim 1 for preparing an organoclay composition, wherein: the clay powder material in the step 1) comprises montmorillonite and sepiolite, wherein the montmorillonite is one or two of sodium-based montmorillonite and artificial sodium montmorillonite.
5. The process for preparing an organoclay composition according to claim 1, wherein: the structural formula of the long-chain alkyl quaternary ammonium salt in the step 4) is as follows:
wherein M is chloride or bromide;
wherein R1 is CH 3 （CH 2 ） n -,n=11～21；
Wherein R2 is CH 3 -or CH 3 （CH 2 ） n -,n=11～21；
Wherein R3 and R4 are CH 3 -。
6. The method of preparing an organoclay composition according to claim 1, wherein: the long-chain alkyl quaternary ammonium salt in the step 4) consists of two components, namely quaternary ammonium salt A and quaternary ammonium salt B, wherein R2 of the quaternary ammonium salt A is CH 3 （CH 2 ） n -n =11 to 21; r2 of quaternary ammonium salt B is CH 3 -; wherein the dosage of the quaternary ammonium salt A is 15-50% of the mass of the clay, and the dosage of the quaternary ammonium salt B is 10-40% of the mass of the clay.
7. The method of preparing an organoclay composition according to claim 1, wherein: and 7) drying and crushing to obtain a product, wherein the water content of the product is less than or equal to 5%, and the fineness of the dry powder is less than or equal to 200 meshes.
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| CN114774093B (en) * | 2022-05-11 | 2023-08-15 | 重庆科技学院 | Organic-inorganic composite polymer for improving shear force of water-based drilling fluid and preparation method thereof |
| CN115260592B (en) * | 2022-08-02 | 2023-07-18 | 浙江丰虹新材料股份有限公司 | Preparation method of nano organic clay compound for polymer |
| WO2024092534A1 (en) * | 2022-11-02 | 2024-05-10 | 浙江丰虹新材料股份有限公司 | High-purity, high-thickening, easy-to-disperse nano montmorillonite used in field of water-based paints and preparation method therefor |
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