CN116037164A - Preparation method and application of solid acid-base catalyst for producing transformer insulating oil - Google Patents
Preparation method and application of solid acid-base catalyst for producing transformer insulating oil Download PDFInfo
- Publication number
- CN116037164A CN116037164A CN202310042526.5A CN202310042526A CN116037164A CN 116037164 A CN116037164 A CN 116037164A CN 202310042526 A CN202310042526 A CN 202310042526A CN 116037164 A CN116037164 A CN 116037164A
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- China
- Prior art keywords
- catalyst
- acid
- stirring
- insulating oil
- organic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 195
- 239000007787 solid Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 239000003930 superacid Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 89
- 235000019198 oils Nutrition 0.000 claims description 89
- 238000003756 stirring Methods 0.000 claims description 84
- 229920000642 polymer Polymers 0.000 claims description 76
- 239000002077 nanosphere Substances 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 55
- 239000002253 acid Substances 0.000 claims description 48
- 239000012065 filter cake Substances 0.000 claims description 45
- 238000005809 transesterification reaction Methods 0.000 claims description 44
- 239000003999 initiator Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 30
- 239000000084 colloidal system Substances 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 25
- 230000032683 aging Effects 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 22
- 239000012018 catalyst precursor Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000011261 inert gas Substances 0.000 claims description 20
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 239000008158 vegetable oil Substances 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- -1 acrylic ester Chemical class 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- 239000000693 micelle Substances 0.000 claims description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 12
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004976 Lyotropic liquid crystal Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002211 L-ascorbic acid Substances 0.000 claims description 6
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002363 hafnium compounds Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052914 metal silicate Inorganic materials 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 claims description 4
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 claims description 4
- 229940075931 sodium dithionate Drugs 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003606 tin compounds Chemical class 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 3
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 3
- PERPYZKCHUBTLM-UHFFFAOYSA-N C(CC)O.[Sn] Chemical compound C(CC)O.[Sn] PERPYZKCHUBTLM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 2
- PMULXWIGWVQPHP-UHFFFAOYSA-N butan-1-ol;tin Chemical compound [Sn].CCCCO PMULXWIGWVQPHP-UHFFFAOYSA-N 0.000 claims description 2
- PSFYVNVZQYWSRW-UHFFFAOYSA-N ethanol;tin Chemical compound [Sn].CCO PSFYVNVZQYWSRW-UHFFFAOYSA-N 0.000 claims description 2
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- INPLRNDUHADSET-UHFFFAOYSA-N butan-1-olate;iron(2+) Chemical compound [Fe+2].CCCC[O-].CCCC[O-] INPLRNDUHADSET-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- QCQJPUZAVFHPMN-UHFFFAOYSA-N iron(2+);propan-2-olate Chemical compound [Fe+2].CC(C)[O-].CC(C)[O-] QCQJPUZAVFHPMN-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
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- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- FPADWGFFPCNGDD-UHFFFAOYSA-N tetraethoxystannane Chemical compound [Sn+4].CC[O-].CC[O-].CC[O-].CC[O-] FPADWGFFPCNGDD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method and application of a solid acid-base catalyst for producing transformer insulating oil. And (3) constructing a catalyst structure framework, leaching a macroporous template in the catalyst framework and loading a solid super acid active site to obtain the solid acid-base catalyst for producing the transformer insulating oil. The solid acid-base catalyst prepared by the invention can realize the acid-base cascade catalytic conversion process by a one-pot method, obtain fine chemical products with high added value, save the multi-step intermediate separation and purification process, have simple process, high atomic efficiency and energy efficiency, are environment-friendly, and greatly save equipment investment and operation cost.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method and application of a solid acid-base catalyst for producing transformer insulating oil.
Background
Insulating oil is widely applied to various electrical equipment (such as transformers, circuit breakers, transformers, bushings and the like) as a liquid medium, and plays roles of insulating, cooling and radiating and extinguishing electric arcs, so that safe operation of the electrical equipment is ensured. The mineral oil product becomes the first choice of insulating oil due to the advantages of low price, good insulating heat dissipation performance and the like, and is widely applied. However, as petroleum refining products, mineral insulating oils have high volatility, low flash point (170-180 ℃), low fire point, poor fire resistance, and once leaked, can cause environmental pollution. In view of this, various national researchers have developed a great deal of research work on alternative products, and non-fuel products such as silicone oil, synthetic esters (pentaerythritol esters), alpha oil, beta oil, poly alpha olefin, HMWH oil (high molecular hydrocarbon oil) and the like have been developed successively. However, these products are generally only used in applications requiring high fire resistance due to the high cost of synthesis. Thus, mineral oils have been firmly dominant in the insulating oil market for many years.
With the improvement of public environmental awareness, the defects of poor biodegradability and easy pollution of mineral insulating oil are becoming more and more the problem, the demand of the market for environment-friendly and degradable insulating oil is becoming more and more urgent, and products with vegetable oil and derivatives thereof as main components become research hot spots in the industry.
In 1999 ABB company, high oleic sunflower oil and high oleic rapeseed oil are used as raw materials, and BIOTEMP vegetable insulating oil (US 5949017) is developed through refining and purification. In 2000, cooper developed a vegetable insulating oil (US 6352655) under the trade name Envirotemp FR3 by purifying natural soybean oil. Meanwhile, L & P company also uses soybean oil as raw material to develop plant insulating oil Biotrans, and M & I Materials company develops Midel eN product. Related studies have also been carried out in germany, japan, france, australia, india etc. to evaluate the feasibility of different vegetable oil raw materials as electrical insulation media after processing.
With the gradual increase of the application scale of the plant insulating oil, corresponding product standards such as ASTM D6871, IEEE Std C57.147 and the like are also internationally established on basic characteristic parameters of the plant insulating oil, and the plant insulating oil is called natural ester insulating medium or natural ester insulating oil.
In addition to natural ester insulating oil products, researchers have also conducted research work on some vegetable oil derivatives. In 2002, the japanese fuji motor synthesizes low-viscosity rapeseed fatty acid ester insulating oil from rapeseed oil and isopropanol, and the viscosity of the low-viscosity rapeseed fatty acid ester insulating oil is about 0.7 times of that of mineral oil. In 2009, palm fatty acid ester insulating oil (PFAE) was prepared from palm oil as a raw material by a two-step transesterification reaction, and an environment-friendly transformer was developed in cooperation therewith. The australian amanulalah et al mixed vegetable insulating oil product with a viscosity lower than that of the natural ester insulating oil by purification processing by mixing vegetable oil with vegetable oil esterification product in a ratio of approximately 1:1, and filed patent AU2006301929B2.
In the domestic aspect, a series of researches are also carried out on Chongqing university, chinese electric department, henan electric department, wuhanzeca and the like. Li Xiaohu and the like are used for processing the transgenic rapeseed oil through alkali refining adsorption, so that a product with good insulating property is obtained, and the ageing property of an oilpaper insulating system is studied. Li Jian and the like improve the insulating property of camellia seed oil by refining and purifying the camellia seed oil, and examine the influence of a plurality of antioxidants on the initial oxidation temperature of the camellia seed oil by using a high Pressure Differential Scanning Calorimetry (PDSC). Zhang Zhaotao and the like are Fe 3 O 4 The nano particles modify rapeseed oil, so that the insulating property of the rapeseed oil is improved (breakdown voltage is improved by 20%). Sun Dagui and the like research the physicochemical electrical properties of the rapeseed oil methyl ester, the viscosity of the rapeseed oil methyl ester is 0.6 times of that of mineral oil, the flash point is higher than 170 ℃, the power frequency breakdown voltage is up to 64 kV, and the rapeseed oil methyl ester has the advantages of low viscosity, good insulating property and the like.
Research has been conducted in this respect by Guangdong Zhuo Yuan New Material science and technology Limited company in combination with research institutions such as the university of West An traffic, the university of northwest, the microbiological institute of Shaanxi, and the like, and the soybean oil is used as the main raw material and has the commodity name RAPO ® Is a natural ester insulating oil product of (CN 102827675 a). Products such as RBD, vinsOil, NP are also respectively introduced by the university of Chongqing, the national electric sciences of the national grid, the electric sciences of the electric company of Henan, and the Wuhan Nanry Limited.
Due to the differences in molecular structure and molecular weight, vegetable oils have the following outstanding advantages over mineral oils:
(1) Excellent electrical insulation properties.
(2) High flash point and high burning point. The flash point of the closed cup of the mineral insulating oil is about 150 ℃, and the flash point of the vegetable oil is generally above 280 ℃, and the flame resistance is far advanced, and is not inferior to that of high-temperature insulating oil such as synthetic alpha oil, silicone oil and the like.
(3) High biodegradability and environmental friendliness.
(4) The raw materials have wide sources and can be regenerated.
Meanwhile, the disadvantages of vegetable oils are also highlighted:
(1) Low temperature performance is poor, the viscosity is high, the condensation point is high, and the cold weather is especially used in cold weather working condition.
(2) The presence of unsaturated bonds in the molecule results in significantly weaker oxidation stability than mineral oil.
Therefore, viscosity reduction, pour point depression and oxidation stability improvement are core problems to be solved in research of the vegetable insulating oil base oil, but are difficult to achieve by physical refining and additive addition (viscosity reducer and pour point depressant), and two aims of improving low-temperature performance and improving oxidation stability are difficult to achieve to a certain extent. Many researchers use short-chain alcohol (methanol, ethanol) transesterification to prepare base oil, and although the physical and electrical properties of the product are good, the flash point and the ignition point are also greatly reduced (< 200 ℃), and the problems of high viscosity and high condensation point are not completely solved, so that a new process for refining the base oil needs to be developed.
To date, there are no products on the market that use vegetable oil derivatives as insulating oil base oils.
In summary, research on plant insulating oil at home and abroad is mainly focused on raw material systems such as soybean oil, rapeseed oil, palm oil, camellia seed oil and the like, but research on cotton seed oil systems with abundant raw materials and low quality and price is little.
The catalysts commonly used in transesterification reactions mainly include three types: acid (homogeneous or solid acid), alkali (homogeneous or solid alkali) and enzyme, wherein the enzyme catalyst has low requirements on raw oil, has the advantages of mild reaction conditions, no side reaction, no waste water generation, easy separation of products and the like, but has high cost and limits the application of the catalyst; the acid catalyst is insensitive to moisture and acid value in the raw oil, but has high reaction temperature and slow reaction rate; the base catalyst has high catalytic efficiency and mild reaction conditions, but is sensitive to moisture and acid value in raw oil, so that separation is difficult. In addition, although the homogeneous (liquid) acid and alkali catalysts have better catalytic performance, the outstanding disadvantage is that the complex and redundant auxiliary processes such as product purification and separation are caused, a large amount of salt-containing wastewater is generated, the catalyst cannot be recycled for multiple times, the production cost is increased, the heavy environmental protection treatment burden is caused, the profit margin of the product is seriously influenced, and the catalyst belongs to an environment-friendly process. The heterogeneous solid acid and base catalyst just overcomes the defects, has the advantages of easy separation and repeated utilization, does not generate waste water and waste, and is environment-friendly in process.
As is known, the indexes of water content, acid value, impurity content and the like of the domestic produced four-stage cottonseed oil are high, and the bottlenecks of active site poisoning, saponification side reaction, difficulty in separating water from oil and the like which occur simultaneously in the transesterification process cannot be overcome by using a single base catalyst.
The preparation of bifunctional catalysts is mostly realized by physical mixing of two single-function catalysts, but the solid acid-base bifunctional integrated catalyst synthesized by adopting the preparation strategy can greatly weaken the catalytic activity of the catalyst due to random distribution among acid-base active sites and contact neutralization effect (macro-chemical incompatibility), and the time sequence of the interaction of reactants and single active sites cannot be regulated, which is particularly critical for a system with impurity side reaction or competitive reaction, because certain component (or impurity) in the reaction system can interfere the reaction of other components, and the yield of target products is reduced.
In recent years, researchers use the principle of space segregation to prepare in situ catalytic sites incompatible with acid and alkali by a sol-gel wet chemistry method into a single material, such as a core-shell nano-structure catalyst, so as to realize the control of a reaction sequence, but the method has two defects: (1) The catalytic activity is limited by factors such as low active site loading, poor accessibility of active sites and the like; (2) The structure is easy to collapse, the stability is poor, and the recycling frequency is limited.
Chinese patent CN 104437632A discloses a macroporous acid-base bifunctional organic solid catalyst, and preparation method and application, adding p-styrenesulfonic acid (SS), water-soluble polymerizable basic monomer, initiator, cross-linking agent and emulsifier into deionized water as water phase, stirring to mix them uniformly; taking paraffin as an oil phase, and dropwise adding the paraffin into an aqueous phase under continuous stirring to prepare a stable high internal phase emulsion; heating to 60-85 ℃ for polymerization reaction for 15-26h, and carrying out Soxhlet extraction on the reactant by acetone and vacuum drying to obtain a polymer; adding the polymer into a dilute acid solution, stirring, filtering, washing with deionized water, and vacuum drying to obtain the macroporous acid-base bifunctional organic solid catalyst, which is used for the chemical reaction of preparing 5-hydroxymethylfurfural from cellulose. The organic polymer macroporous solid acid-base catalyst prepared by the patent mainly has the following defects: (1) The acid sites are formed by acid impregnation, so that the binding force between the acid sites and the catalyst matrix material is weak, and the acid sites are easy to fall off and lose activity in the use process; (2) The two active sites of acid and alkali are mixed spatially, which is easy to cause poisoning and deactivation of the catalyst.
Chinese patent CN 105642345a discloses a preparation method of a hydrophobic hierarchical pore solid acid-base bifunctional catalyst by using alkaline functionalized hydrophobic nanoparticles (S-NH 2 ) And span80 (span 80) as an emulsifier to prepare a stable Pickering high internal phase emulsion, wherein the aqueous phase comprises deionized water and potassium sulfate, the oil phase comprises Divinylbenzene (DVB), 1-hexene, trimethylolpropane trimethacrylate (TMPTMA) and 2,2' -Azobisisobutyronitrile (AIBN), and then a hydrophobic hierarchical pore solid acid-base bifunctional catalyst (PAPCs) is obtained through emulsion polymerization and sulfonation processes for the chemical reaction of cellulose to prepare 5-hydroxymethylfurfural. This patent has mainly the following problems: (1) The catalyst is an organic polymer material, cannot bear high-temperature heat treatment, and has limited catalyst regeneration effect; (2) The acidic sites are formed by acid impregnation and drying, and cannot be subjected to high-temperature heat treatment, so that the binding force between the acidic sites and the catalyst matrix material is weak, and the acidic sites are easy to fall off in the use process to lose activity.
Chinese patent CN 102682869A discloses a vegetable insulating oil and a preparation method thereof, wherein the vegetable insulating oil takes refined vegetable oil as a raw material, and carries out transesterification reaction with low molecular alcohol, after the reaction is stopped, refining washing, reduced pressure distillation for removing alcohol, decoloring, reducing acid, filtering, then carrying out deep water removal, and finally adding an antioxidant and a pour point depressant. The vegetable insulating oil prepared by the patent mainly has the following defects: (1) The transesterification reaction is mainly carried out by adopting small molecular alcohol, so that the obtained insulating oil has low flash point and ignition point and general fireproof performance; (2) The prepared insulating oil has higher pour point and can not be used for working conditions with harsh requirements on low-temperature performance, such as northeast, northwest, qinghai-Tibet plateau and the like.
Chinese patent CN 102827675a discloses a method for preparing environment-friendly insulating oil from vegetable oil or recovered oil, comprising the following steps: acid value is 4-100 mgKOH.g -1 Dewaxing vegetable oil or recovered oil at low temperature to obtain oil with reduced condensation point; catalytic esterification is carried out on the oil with the condensation point reduced until the acid value is less than or equal to 10mgKOHg -1 The method comprises the steps of carrying out a first treatment on the surface of the Performing alkali neutralization reaction on the condensation point reducing oil to obtain acid reducing oil; mixing and decoloring the deacidification oil to obtain a decolored oil; vacuum distilling the decolorized oil, heating to 200-220 deg.c, and vacuum deodorizing with steam to obtain deodorized oil; carrying out reduced pressure distillation on the deodorized oil again to obtain the dehydrated oil; and fully mixing the water-removed oil with 0.1-0.5 wt% of antioxidant to obtain the environment-friendly insulating oil. This patent has mainly the following problems: the transesterification reaction adopts a homogeneous liquid alkali catalyst, which cannot be reused, and a large amount of waste brine and solid wastes are generated in the process of separating and purifying the product, so that the transesterification reaction is environment-friendly.
Disclosure of Invention
The invention aims to provide a preparation method of a solid acid-base catalyst for producing transformer insulating oil, the prepared catalyst has high activity and low performance attenuation, can realize a one-pot cascade catalytic conversion process, obtain fine chemical products with high added value, save a multi-step intermediate separation and purification process, greatly simplify the process, greatly improve the atomic efficiency and the energy efficiency, greatly reduce the equipment investment and the operation cost, and has no waste water and waste emission in the whole production process, thus having good economic benefit and wide social benefit; the invention also provides application of the solid acid-base catalyst for producing the transformer insulating oil, which is used for producing the transformer insulating oil by transesterification of vegetable oil.
The preparation method of the solid acid-base catalyst for producing transformer insulating oil comprises the following steps:
(1) Construction of catalyst structure framework
a. Preparation of basic catalyst matrix
Firstly adding an amphiphilic block copolymer into deionized water, adding acid for acidification, uniformly mixing, standing, self-assembling to form a lyotropic liquid crystal micelle, then adding metal nitrate and silicate, and stirring to obtain a catalyst alkaline matrix solution A;
b. preparation of monodisperse polymer colloid nanospheres used as macroporous hard templates
Under the protection of inert gas and stirring conditions, dropwise adding an initiator into the polymer monomer and ultrapure water for reaction to obtain white polymer colloid nanospheres, washing the white polymer colloid nanospheres, and drying in vacuum to obtain nanospheres B;
or under the condition of inert gas protection and stirring, dropwise adding an initiator into a polymer monomer, a coupling monomer, an emulsifier and ultrapure water for reaction to obtain white polymer colloid nanospheres, washing the white polymer colloid nanospheres, and drying in vacuum to obtain nanospheres B;
c. blending and gelling of catalyst alkaline matrix and macroporous template
Mixing the catalyst alkaline matrix solution A and the nanospheres B, stirring, homogenizing and aging to obtain a catalyst alkaline framework C;
(2) Leaching of macroporous template in catalyst framework and loading of solid super acid active site
a. Leaching of macroporous templates in catalyst frameworks
Adding the catalyst alkaline framework C into a good solvent of a polymer hard template, stirring, leaching, filtering and washing a filter cake to obtain a catalyst precursor D after the hard template is removed;
b. loading of acidic active sites in catalysts
Adding the catalyst precursor D into an organic solvent, adding an organic metal compound for reaction under the conditions of inert gas protection and stirring, vacuum filtering to obtain a filter cake, and drying to obtain a dry filter cake;
hydrolyzing the dry filter cake to obtain a hydrolysate filter cake, and drying in vacuum to obtain powder E;
under the condition of room temperature and stirring, the powder E is immersed and treated by an alcohol solution of ammonium sulfate, a filter cake is obtained by vacuum suction filtration, and a solid acid-base catalyst for producing the transformer insulating oil is obtained by vacuum drying and roasting.
The amphiphilic block copolymer in step (1) a is a polyether having the structure PEO-PPO-PEO; the amphiphilic block copolymer comprises at least P123 and may further comprise one or more of L123, P103, L62, F127 or F68. L123 is preferably L123 manufactured by BASF corporation.
The acid in the step (1) a is one of inorganic acid or organic acid, and acidizing is carried out until the pH value is=0-3.
The mixing temperature in the step (1) a is room temperature-60 ℃.
The mass ratio of deionized water to the amphiphilic block copolymer in the step (1) a is 3:2-4.5.
The metal nitrate in the step (1) a is one or more of alkaline earth metal nitrate, transition metal nitrate or rare earth metal nitrate.
The silicate in the step (1) a is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
The stirring speed in the step (1) a is 1000-2000rpm, and the stirring time is 15-30 minutes.
The mole ratio of the amphiphilic block copolymer, the metal nitrate and the silicate in the step (1) a is 1:5-8:60-110.
The polymer monomer in the step (1) b is one or more of styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene, p-isobutyl styrene and p-tert-butyl styrene.
The coupling monomer in the step (1) is one of maleic anhydride or acrylic ester, and the dosage of the coupling monomer is 1.5-6% of the total mass of the polymer monomer.
The emulsifier in the step (1) is alkylphenol ethoxylate OP-10 or sodium dodecyl sulfate, and the dosage of the emulsifier is 0.5-2% of the total mass of the polymer monomer.
The initiator in the step (1) b is one of a single initiator or a composite initiator; wherein the single initiator is one of potassium persulfate, ammonium persulfate or hydrogen peroxide, and the composite initiator is one of potassium persulfate, ammonium persulfate or hydrogen peroxide and one or more of sodium sulfite, sodium bisulphite, sodium dithionate or L-ascorbic acid; the initiator is used in an amount of 0.1 to 7 percent of the total mass of the polymer monomers.
The mass ratio of the polymer monomer to the ultrapure water in the step (1) b is 1:6-10.
The reaction temperature in step (1) b is 75-85 ℃.
The drop time of the initiator in the step (1) b is 30-120 minutes.
The washing times in the step (1) b are 3-6 times.
The vacuum drying temperature in the step (1) b is 60-120 ℃.
The stirring time in the step (1) c is 15-30 minutes.
The ageing time in step (1) c is 24-72 hours.
In the step (1), the mass ratio of the catalyst alkaline matrix solution A to the nanospheres B is 3-4:2.
The good solvent in the step (2) a is one of toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetone, dichloromethane or chloroform.
The leaching temperature in the step (2) a is-5 to 0 ℃, and the leaching time is 20 to 40 seconds.
The washing in the step (2) a adopts cold good solvent washing, and the washing times are 2-3 times.
The mass ratio of the catalyst basic skeleton C to the good solvent in the step (2) a is 1:6.5-9.
The stirring speed in the step (2) a is 800-1200rpm.
The organic solvent in the step (2) b is one of cyclohexane, hexane, carbon tetrachloride, propanol, isopropanol, tetrahydrofuran, ethyl acetate, chloroform, methyl ethyl ketone or acetone.
The organometallic compound in the step (2) b is one or more of an organotitanium compound, an organozirconium compound, an organohafnium compound, an organoiron compound or an organotin compound; the organic titanium compound is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate or tetrabutyl titanate, the organic zirconium compound is one of tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate or tetrabutyl zirconate, the organic hafnium compound is one of tetraethyl hafnate, tetrapropyl hafnate, tetraisopropyl hafnate or tetrabutyl hafnate, the organic iron compound is one of ferric ethanol, ferric n-propanol, ferric isopropanol or ferric n-butanol, and the organic tin compound is one of tin ethanol, tin n-propanol, tin isopropanol or tin n-butanol.
In the step (2), the mass ratio of the catalyst precursor D to the organic solvent is 1:14-30, and the mass ratio of the catalyst precursor D to the organometallic compound is 1-4:1.
The reaction temperature in the step (2) is 50-80 ℃ and the reaction time is 24-48 hours.
The soaking time in the step (2) b is 2-6 hours.
And (3) roasting in the step (2) at 400-700 ℃ for 4-6 hours.
The stirring speed in the step (2) b is 800-1200rpm.
The concentration of the alcoholic solution of ammonium sulfate in the step (2) is 0.1-0.4mol/L.
The application of the catalyst prepared by the preparation method of the solid acid-base catalyst for producing transformer insulating oil is used for producing transformer insulating oil by vegetable oil transesterification.
The vegetable oil is cotton seed oil.
The preparation method of the solid acid-base catalyst for producing transformer insulating oil comprises the following specific steps:
(1) Construction of catalyst structure framework
a. Preparation of basic catalyst matrix
Firstly adding quantitative amphiphilic block copolymer into deionized water, adding acid for acidification, then placing into a variable speed vortex oscillation mixer, controlling a certain temperature for uniform mixing, taking out and standing, taking the amphiphilic block copolymer as a soft template for self-assembly to form lyotropic liquid crystal micelle, then quantitatively adding metal nitrate and silicate, and stirring to form a catalyst alkaline matrix solution A for later use. The silicate is hydrolyzed under the action of the amphiphilic block copolymer surfactant soft template to form an SBA-15 mesoporous silica structure;
The acidity of the solution is controlled in the range of ph=0-3, preferably 1.5-2.5, in particular in the range of ph=0-3, in the medium strong acid range, before shaking mixing. Inorganic acid or organic acid can be used for adjusting acidity, such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, etc.
The mixing temperature is controlled in the range of room temperature to 60℃and preferably 45 to 50 ℃.
The metal nitrate is one of alkaline earth metal nitrate, transition metal nitrate or rare earth metal nitrate, such as magnesium nitrate, calcium nitrate, copper nitrate, nickel nitrate, manganese nitrate, lanthanum nitrate, cerium nitrate, samarium nitrate, etc.
The silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
After the addition of the metal nitrate and silicate, the stirring speed is 1000-2000rpm, preferably 1500rpm; the stirring time is 15 to 30 minutes, preferably 20 to 25 minutes.
b. Preparation of monodisperse polymer colloid nanospheres used as macroporous hard templates
When preparing the homopolymer nanospheres, the preparation method is as follows:
firstly, removing polymerization inhibitor in polymer monomers by a conventional method, adding purified monomers into ultrapure water, protecting by inert gas, dropwise adding an initiator while stirring at a certain temperature, continuously stirring for 24-48 hours after the dropwise adding is finished until white polymer colloid nanospheres are generated, separating the polymer nanospheres by a high-speed refrigerated centrifuge, washing and vacuum drying to obtain nanospheres B; wherein the polymer monomer is one of styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene, p-isobutyl styrene or p-tert-butyl styrene.
When preparing the block copolymer nanospheres, the preparation method is as follows:
firstly, removing polymerization inhibitor in polymer monomer and coupling monomer by using a conventional method, then adding purified monomer and emulsifier into ultrapure water, protecting by inert gas, dropwise adding an initiator while stirring at a certain temperature, continuing stirring for 24-48 hours after the dropwise adding is finished until white polymer colloid nanospheres are generated, separating the polymer nanospheres by using a high-speed refrigerated centrifuge, washing and vacuum drying to obtain nanospheres B; wherein the polymer monomer is two of styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene, p-isobutyl styrene or p-tert-butyl styrene.
The block copolymer nanosphere has a structure of A (B-o-A) nB type, wherein A, B is a polymerized monomer, and o is a coupling monomer; wherein the molar ratio of the polymerized monomer A to the polymerized monomer B is 1:10-10:1.
When the segmented copolymer nanospheres are synthesized, maleic anhydride or acrylic ester can be used as a coupling monomer, wherein the preferable acrylic ester is one of ethyl acrylate, butyl acrylate, hydroxyethyl acrylate or hydroxypropyl acrylate, and the dosage is 1.5-6% of the total mass of the polymer monomer, and is preferably 3-4% of the total mass of the polymer monomer.
When the segmented copolymer nanospheres are synthesized, alkylphenol ethoxylates OP-10 or sodium dodecyl sulfate SDS can be used as an emulsifier, and the dosage is 0.5-2% of the total mass of the polymer monomers, preferably 1% of the total mass of the polymer monomers.
The polymerization temperature is 75-85 ℃.
The polymerization initiator comprises a single initiator and a compound initiator, wherein the single initiator comprises potassium persulfate, ammonium persulfate and hydrogen peroxide; the composite initiator is a redox initiation system formed by one or more of persulfate (potassium and ammonium) and (sulfite) (sodium sulfite, sodium bisulphite and sodium dithionate) and L-ascorbic acid, and the redox initiation system formed by one or more of hydrogen peroxide and (sulfite) (sodium sulfite, sodium bisulphite and sodium dithionate) and L-ascorbic acid.
The initiator is used in an amount of 0.1 to 7% by weight, preferably 1 to 4% by weight, based on the total mass of the polymer monomers.
The dripping speed of the initiator is controlled by the dripping time, the total dripping time is controlled to be 30-120 minutes, and the total dripping time is preferably 60-90 minutes. The initiator can be added dropwise in sections, and the temperature of each section is controlled to be stepwise, such as 75 ℃, 80 ℃ and 85 ℃, so that the uniformity and isotropy of the preparation size of the polymer colloid sphere are improved.
Stirring rate control protocol: in the initial stage of the polymerization reaction, in the process of dropwise adding the initiator, the stirring speed is controlled at 800-1200rpm, preferably 1000rpm; after the initiator is added dropwise, the stirring speed is controlled at 300-800rpm, preferably 600rpm, before the polymer colloid balls appear; during the aging process after the formation of the polymer colloid spheres, the stirring rate is controlled to 100-500rpm, preferably 200-300rpm.
The centrifuge speed for separating nanospheres ranges from 8000 to 30000rpm, preferably from 15000 to 20000rpm.
The washing times of the nanospheres are 3-6 times, preferably 5 times.
The vacuum drying temperature is 60-120deg.C, preferably 80deg.C.
c. Blending and gelling of catalyst alkaline matrix and macroporous template
Quantitatively mixing the prepared catalyst alkaline matrix solution A and nanospheres B, stirring at high speed for 15-30 minutes, homogenizing, removing hydrolyzed micromolecular products by vacuum rotary evaporation, gelatinizing and solidifying in room temperature air, and aging for 24-72 hours to obtain the catalyst alkaline skeleton C.
(2) Leaching of macroporous template in catalyst framework and loading of solid super acid active site
a. Leaching of macroporous templates in catalyst frameworks
And quantitatively adding the catalyst alkaline skeleton C prepared in the last step into a good solvent of a polymer hard template, stirring at a medium speed (800-1200 rpm), leaching at a low temperature for 30 seconds, filtering, washing a filter cake with a cold good solvent for 2-3 times, and repeating the leaching process for 3-6 times to remove the polymer hard template as much as possible, thereby obtaining the catalyst precursor D after the removal of the hard template.
The good solvent is one of toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetone, dichloromethane or chloroform.
The leaching temperature is controlled between-5 and 0 ℃.
b. Loading of acidic active sites in catalysts
Quantitatively adding the catalyst precursor D into a nonpolar or weak polar organic solvent, controlling the temperature to be 50-80 ℃, protecting by inert gas, adding an organic metal compound while stirring, continuously stirring and reacting for 24-48 hours, vacuum-filtering to obtain a filter cake, and drying.
And (3) hydrolyzing the dry filter cake, stirring at a medium speed (800-1200 rpm) for 30-60 minutes, vacuum-filtering to obtain a hydrolysate filter cake, and vacuum-drying for 12 hours to obtain powder E.
Under the condition of stirring at room temperature and medium speed (800-1200 rpm), the powder E is immersed in an alcohol solution of ammonium sulfate for 2-6 hours, then vacuum filtration is carried out to obtain a filter cake, vacuum drying is carried out at 120 ℃ for 8 hours, then the filter cake is baked for 4-6 hours at 400-700 ℃ in a box-type furnace, polyether in the material is burned off, and the solid acid-base catalyst for producing the transformer insulating oil is obtained.
The nonpolar or low-polarity organic solvent is one of cyclohexane, hexane, carbon tetrachloride, propanol, isopropanol, tetrahydrofuran, ethyl acetate, chloroform, methyl ethyl ketone or acetone.
The organic metal compound is one or more of organic titanium compounds, organic zirconium compounds, organic hafnium compounds, organic iron compounds and organic tin compounds, wherein the organic titanium compounds comprise tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate and the like; organozirconium compounds include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, and the like; organohafnium compounds include tetraethyl hafnate, tetrapropyl hafnate, tetraisopropyl hafnate, tetrabutyl hafnate, and the like; the organic iron compound comprises iron ethoxide, iron n-propoxide, iron isopropoxide, iron n-butoxide and the like; the organotin compound includes tin ethoxide, n-propoxide, isopropoxide, n-butoxide, etc. The organic metal compound used in the preparation process is one or the combination of two of the organic metal compounds listed above, and the mixing proportion is adjustable.
Pores with a pore diameter of 2-50nm are called mesopores, and pores with a pore diameter of more than 50nm are called macropores. The catalyst particles prepared by the invention have interconnected macroporous and mesoporous structures, wherein the macropores exist on the surface of the catalyst in an open structure, the mesoporous structures are distributed among the macroporous structures, and the acidic and alkaline active sites are respectively and highly dispersed in the macropores and the mesopores in the form of oxides. In the process of preparing the transformer insulating oil by using the one-pot transesterification with the cottonseed oil as the raw material, the problem of catalyst poisoning and deactivation caused by the over-high acid value of the raw material (high fatty acid content) can be effectively prevented, the limiting requirement on the acid value of the raw material is reduced, and the prepared transformer insulating oil has excellent indexes.
Pore-forming mechanism of the present invention:
it is known that an amphiphilic block copolymer such as P123 is a high molecular compound formed by linking a hydrophilic PEO segment and a hydrophobic PPO segment together by covalent bonds, has good nonionic surface activity, under the conditions of a certain proportion, pH and the like, the hydrophilic segment and the hydrophobic segment in the amphiphilic block copolymer molecule can thermodynamically and spontaneously form a large number of H1 type micelle structures, a large number of micelles are uniformly dispersed in a solution, a metal nitrate aqueous solution is wrapped in the micelles by the hydrophilic segment, silicate is isolated between the micelles by the hydrophobic segment, the amphiphilic block copolymer molecule plays a role of a soft template, silicate is hydrolyzed to form an SBA-15 type mesoporous silica structure, a polymer micelle of metal nitrate is sealed in each mesoporous, the soft template amphiphilic block copolymer molecule is removed by the final step of roasting, the metal nitrate is decomposed into metal oxide, and only SBA-15 type mesoporous SiO is left in the alkaline matrix part of the catalyst 2 The cells and the metal oxides contained therein. Due to the mediumThe pore size is small (around 4nm, see table 1, fig. 3), so the metal oxide exists in the form of highly dispersed amorphous state within the mesoporous material, as clearly seen in the wide angle XRD diffraction pattern in fig. 2.
After the catalyst alkaline matrix and the polymer nanospheres are mixed, homogenized, steamed and gelled and solidified, spherical hard contact is formed between the alkaline matrix and the nanospheres, and after the polymer nanospheres are removed by multiple solvent leaching and dissolution, a macroporous structure is formed on the hard contact spherical surface, and the macropores are all open structures, namely, are positioned on the surface of the catalyst structural framework and are in direct contact with the environment. Then, the hydroxylated metal oxide is loaded into a macroporous structure through hydrolysis of the metal organic compound, and the macroporous structure material loaded with the sulfated metal oxide (solid acid) is obtained through impregnation and roasting of ammonium persulfate.
As the alkaline matrix is hydrolyzed, siO of SBA-15 is formed 2 The spherical shape of the mesoporous pore canal structure, where the macroporous pore canal is located, is directly connected with the alkaline matrix, so that the macroporous pore canal and the mesoporous pore canal in the catalyst prepared by roasting are necessarily communicated. This conclusion gives a perfect verification of the data of the transesterification of cottonseed oil (data of examples 5, 8 in Table 4) because, as previously mentioned, the basic active sites of catalytic effect on the transesterification are present only in the mesopores of the catalyst and the mesopores are all internal to the material, and if the macropores and mesopores are not interconnected, the cottonseed oil cannot enter the mesopores to complete the transesterification.
The catalytic mechanism of the solid acid-base catalyst of the invention is as follows:
in the solid acid-base catalyst, alkaline active sites are dispersed in mesopores, the mesopores are positioned in the catalyst material, acidic active sites are dispersed in macropores, and the macropores are positioned on the surface of the catalyst material and are in an open structure and are in direct contact with the environment. Therefore, in order for the cottonseed oil to undergo transesterification, the cottonseed oil must enter the catalyst material through macropores, then diffuse into the mesopores along the passages between the macropores and the mesopores, reach the alkaline active sites, undergo transesterification, and the product diffuses out of the catalyst material.
The reasons for the high catalytic activity and slow performance decay of the solid acid-base catalyst of the invention are mainly 2: (1) As clearly shown in the wide-angle XRD pattern of FIG. 2, the basic active sites and the acidic active sites are highly dispersed, amorphous and approximate to the state of a monoatomic catalyst, so that the availability of the active sites is approximate to 100%, and the catalytic effect can be simultaneously exerted; (2) The acidic and alkaline sites of the common solid acid-base catalyst are generally mixed in space structure, if a large amount of free fatty acid exists in the cottonseed oil (the acid value is high), when the cottonseed oil raw material is contacted with the catalyst, the free fatty acid in the cottonseed oil can cover the acidic and alkaline active sites indiscriminately at the same time, thereby poisoning the alkaline active catalytic sites, failing to catalyze the transesterification reaction, and leading to low catalytic performance and rapid performance attenuation. The catalyst synthesized by the invention has the advantages that the acidic active sites and the alkaline active sites are not mixed in space distribution, the acidic active sites are positioned on the surface of the macropores of the catalyst material, the alkaline active sites are distributed in the internal mesopores of the catalyst material, when the high acid value cottonseed oil raw material is contacted with the catalyst, the acidic sites in the macropores of the surface are contacted first, the free fatty acid in the cottonseed oil is subjected to esterification reaction under the catalysis of the acidic sites to generate esters which are non-toxic to the alkaline sites, then the cottonseed oil passes through the channel between the macropores and the mesopores to enter the mesopores, at the moment, the raw material does not contain the free fatty acid which is toxic to the alkaline active sites, the glyceride in the cottonseed oil starts to generate ester exchange reaction under the catalysis of the alkaline sites to generate new esters, and the catalysis performance can be maintained to be efficient even after multiple use, so the unique space structure of the catalyst brings the advantages of high catalytic activity and slow performance.
The invention adopts the cottonseed oil as the raw material, and prepares the cottonseed oil derivative insulating oil with excellent low-temperature performance and high ignition point flash point through the transesterification between the cottonseed oil and branched chain alcohol.
The beneficial effects of the invention are as follows:
the solid acid-base catalyst prepared by the invention can realize the acid-base cascade catalytic conversion process by a one-pot method, obtain fine chemical products with high added value, save the multi-step intermediate separation and purification process, have simple process, high atomic efficiency and energy efficiency, are environment-friendly, and greatly save equipment investment and operation cost. In the process of preparing the transformer insulating oil by using the one-pot transesterification with the cottonseed oil as the raw material, the problem of catalyst poisoning and deactivation caused by the over-high acid value of the raw material (high fatty acid content) can be effectively prevented, the limiting requirement on the acid value of the raw material is reduced, and the prepared transformer insulating oil has excellent indexes.
Drawings
Fig. 1 is a small angle XRD diffractogram of the catalyst prepared in example 1.
Fig. 2 is a wide angle XRD diffractogram of the catalyst prepared in example 1.
FIG. 3 is a pore size distribution plot of the catalyst prepared in example 1.
FIG. 4 is N of the catalyst prepared in example 1 2 Physical adsorption and desorption isotherm plot.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Adding 56 g of nonionic amphiphilic block copolymer (48 g of P123 and 8 g of P103) into 52 g of deionized water, acidifying with nitric acid to pH=1.0, putting into a variable speed vortex mixer, uniformly mixing at 50 ℃, taking out, standing, self-assembling to form lyotropic liquid crystal micelles, and adding 14.2 g of Ca (NO) 3 ) 2 ·4H 2 O and 185ml of ethyl orthosilicate are stirred at 1500rpm for 25 minutes to form a homogeneous basic matrix solution A of the catalyst 1 And (5) standby application.
Removing polymerization inhibitor in polymer monomer p-methylstyrene by conventional method, adding 168 g of purified monomer into 1370 ml of ultrapure water, introducing inert gas for protection, and respectively dripping redox initiator ammonium persulfate and sodium bisulfite system under stirring at 1000rpmThe dropping amount of sodium bisulfate is 3 percent and 0.7 percent of the mass of the polymer monomer respectively, the dropping process is divided into three stages, each stage is 30 minutes, and the temperature control of the three stages is 75 ℃, 80 ℃ and 85 ℃ respectively. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process of the white polymer colloid nanospheres after molding, the stirring speed is controlled at 200rpm, and the aging process is stirred for 12 hours. Then separating out polymer nanospheres by a high-speed refrigerated centrifuge at a speed of 15000rpm, washing for 5 times and vacuum drying at 80 ℃ to obtain the product, namely the poly (p-methylstyrene) nanospheres B 1 。
150 g of solution A prepared as described above were mixed 1 And 75 g nanospheres B 1 Homogenizing under high speed stirring for 30 min, vacuum rotary evaporating to remove hydrolyzed small molecular product, gelatinizing and solidifying in room temperature air, aging for 48 hr to obtain catalyst basic skeleton C 1 。
30 g of catalyst basic skeleton C 1 Adding into 250 ml of xylene, leaching at 1000rpm and-5deg.C for 30 seconds, filtering, washing filter cake with cold xylene solvent for 3 times, repeating the leaching process for 4 times to remove hard template of poly (p-methylstyrene) as much as possible, and marking the obtained product as catalyst precursor D 1 。
8 g of catalyst precursor D 1 Adding the mixture into 200 ml of hexane, controlling the temperature to be 80 ℃, introducing inert gas for protection, adding 4 g of tetrapropyl zirconate while stirring, continuously stirring for reaction for 24 hours, vacuum filtering to obtain a filter cake, and drying. Then putting the dry filter cake into 200 ml of deionized water, stirring at 1000rpm for 60 minutes, vacuum-pumping and filtering to obtain a hydrolysate filter cake, and vacuum-drying for 12 hours to obtain powder E 1 。
Impregnating the powder E with 0.3M ammonium sulfate alcohol solution at room temperature and stirring at 800rpm 1 After 3 hours, vacuum filtering to obtain a filter cake, vacuum drying at 120 ℃ for 8 hours, then roasting for 5 hours at 500 ℃ in a box-type furnace, and burning polyether in the material to obtain mesoporous CaO-macroporous ZrSO 5 "solid acid-base double function integrated catalyst".
Example 2
78 g of nonionic amphiphilic block copolymer (66 g of P123 and 12 g of F127) are added into 52 g of deionized water, acidified to pH=0 by sulfuric acid, then put into a variable speed vortex mixer to be uniformly mixed at 30 ℃, taken out, stood still and self-assembled to form lyotropic liquid crystal micelles, and then 15.9 g of Mg (NO) is added 3 ) 2 ·6H 2 O and 111ml of methyl orthosilicate are stirred at 2000rpm for 20 minutes to form a homogeneous basic matrix solution A of the catalyst 2 And (5) standby application.
Removing polymerization inhibitor in polymer monomer styrene by conventional method, adding 137 g of purified monomer into 1370 ml of ultrapure water, introducing inert gas for protection, and dripping redox initiator hydrogen peroxide and L-ascorbic acid system under stirring at 1000rpm, wherein the dripping amount of hydrogen peroxide and L-ascorbic acid is 1% and 0.25% of the mass of polymer monomer, the dripping process is divided into two stages, each stage is 45 minutes, and the temperature control of the two stages is 75 ℃ and 85 ℃. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process of the white polymer colloid nanospheres after molding, the stirring speed is controlled at 300rpm, and the aging process is stirred for 12 hours. Then separating polymer nanospheres by a high-speed refrigerated centrifuge at 20000rpm, washing for 3 times and vacuum drying at 120 ℃, and obtaining the product, namely polystyrene nanospheres B 2 。
150 g of the solution prepared above were mixed 2 And 100 grams nanospheres B 2 Homogenizing under high speed stirring for 25 min, vacuum rotary evaporating to remove hydrolyzed small molecular product, gelatinizing and solidifying in room temperature air, aging for 24 hr to obtain catalyst basic skeleton C 2 。
30 g of catalyst basic skeleton C 2 Adding into 227 ml of dimethylbenzene, leaching at a stirring speed of 800rpm at-3 ℃ for 20 seconds, filtering, washing a filter cake with cold dimethylbenzene solvent for 2 times, repeating the leaching process for 6 times to remove the polystyrene hard template as much as possible, and marking the obtained product as a catalyst precursor D 2 。
8 g of catalyst precursor D 2 Added into 305 ml of isopropanol2 g of tetrabutyl zirconate is added while stirring under the protection of inert gas when the temperature is controlled at 70 ℃, the reaction is continued for 24 hours while stirring, the filter cake is obtained by vacuum filtration, and the filter cake is dried. Then putting the dry filter cake into 200 ml of deionized water, stirring for 60 minutes at 800rpm, vacuum-filtering to obtain a hydrolysate filter cake, and vacuum-drying for 12 hours to obtain powder E 2 。
Impregnating the powder E with 0.4M ammonium sulfate alcohol solution at room temperature and 900rpm 2 After 2 hours, vacuum filtering to obtain a filter cake, vacuum drying at 120 ℃ for 8 hours, roasting for 4 hours at 700 ℃ in a box-type furnace, and burning polyether in the material to obtain mesoporous MgO-macroporous ZrSO 5 "solid acid-base double function integrated catalyst".
Example 3
Adding 35 g of nonionic amphiphilic block copolymer (28 g of P123 and 7 g of L62) into 52 g of deionized water, acidifying with hydrochloric acid to pH=3.0, putting into a variable speed vortex mixer, uniformly mixing at 40 ℃, taking out, standing, self-assembling to form lyotropic liquid crystal micelles, and adding 9.2 g of Ca (NO 3 ) 2 ·4H 2 O, 78, ml propyl orthosilicate, stirring at 1000rpm for 15 minutes to form a uniform basic catalyst base solution A 3 And (5) standby application.
Removing polymerization inhibitor in polymer monomer p-isobutyl styrene by conventional method, adding 228 g of purified monomer into 1370 ml of ultrapure water, introducing inert gas for protection, and dripping redox initiator ammonium persulfate and sodium bisulphite respectively under stirring at 1000rpm for 60 min, wherein the dripping amount of ammonium persulfate and sodium bisulphite is 5.6% and 1.4% of the mass of the polymer monomer, and the dripping process is divided into two stages, each stage is 30 min, and the temperature control of the two stages is 75 ℃ and 85 ℃. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process of the white polymer colloid nanospheres after molding, the stirring speed is controlled at 300rpm, and the aging process is stirred for 12 hours. Then separating polymer nanospheres by a high-speed refrigerated centrifuge at 15000rpm, washing for 6 times and vacuum drying at 60 ℃ to obtain the product, namely the poly-p-isobutyl styrene Nanospheres B 3 。
120 g of solution A prepared as described above were mixed 3 And 72 grams of nanospheres B 3 Homogenizing under high speed stirring for 20 min, vacuum rotary evaporating to remove hydrolyzed small molecular product, gelatinizing and solidifying in room temperature air, aging for 36 hr to obtain catalyst basic skeleton C 3 。
30 g of catalyst basic skeleton C 3 Adding into 280 ml toluene, leaching at 1200rpm and 0deg.C for 20 s, filtering, washing filter cake with cold toluene solvent for 2 times, repeating the leaching process for 5 times to remove hard template of poly-p-isobutylstyrene as much as possible, and marking the obtained product as catalyst precursor D 3 。
8 g of catalyst precursor D 3 Adding the mixture into 151 ml of cyclohexane, controlling the temperature to be 60 ℃, introducing inert gas for protection, adding 8 g of tetrabutyl titanate while stirring, continuously stirring and reacting for 36 hours, vacuum filtering to obtain a filter cake, and drying. Then putting the dry filter cake into 200 ml of deionized water, stirring at 1200rpm for 60 minutes, vacuum-pumping and filtering to obtain a hydrolysate filter cake, and vacuum-drying for 12 hours to obtain powder E 3 。
Impregnating the powder E with 0.1M ammonium sulfate alcohol solution at room temperature and 1000rpm 3 After 6 hours, vacuum filtering to obtain a filter cake, vacuum drying at 120 ℃ for 8 hours, then roasting in a box furnace at 400 ℃ for 6 hours, and burning polyether in the material to obtain mesoporous CaO-macroporous TiSO 5 "solid acid-base double function integrated catalyst".
Example 4
Adding 65 g of nonionic amphiphilic block copolymer (58 g of P123 and 7 g of F68) into 52 g of deionized water, acidifying with acetic acid to pH=2.0, putting into a variable-speed vortex mixer, uniformly mixing at 60 ℃, taking out, standing, self-assembling to form lyotropic liquid crystal micelles, and adding 20.4 g of Mg (NO 3 ) 2 ·6H 2 O and 253 ml butyl orthosilicate, and stirred at 2000rpm for 30 minutes to form a uniform basic catalyst base solution A 4 And (5) standby application.
The monomers ethyl acrylate, styrene and para-methyl were removed by conventional methodsThe polymerization inhibitor in the styrene is synthesized into a block copolymer A (B-o-A) nB by taking alkylphenol ethoxylates OP-10 as an emulsifier, ethyl acrylate as a coupling monomer and styrene and p-methylstyrene as comonomers, wherein A, B is styrene and p-methylstyrene respectively, and o is the coupling monomer ethyl acrylate. 151.2 g of purified styrene monomer, 19 g of p-methylstyrene monomer, 6.8 g of ethyl acrylate monomer and 1.7 g of alkylphenol ethoxylate (OP-10) are added into 1370 ml of ultrapure water, inert gas is introduced for protection, a redox initiator of ammonium persulfate and sodium bisulfite system is respectively added dropwise under stirring at the speed of 1000rpm, the adding amount of the ammonium persulfate and the sodium bisulfite is respectively 4 percent and 1 percent of the total mass of the polymer monomer, the adding process is 60 minutes, and the temperature is controlled at 80 ℃. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process after the white polymer colloid nanospheres are formed, the stirring speed is controlled at 250rpm, and the aging process is stirred for 12 hours. Then separating polymer nanospheres by a high-speed refrigerated centrifuge at 20000rpm, washing for 5 times and vacuum drying at 80 ℃, and obtaining the product, namely the segmented copolymer nanospheres B 4 。
150 g of solution A prepared as described above were mixed 4 And 83 g nanospheres B 4 Homogenizing under high speed stirring for 15 min, vacuum rotary evaporating to remove hydrolyzed small molecular product, gelatinizing and solidifying in room temperature air, aging for 72 hr to obtain catalyst basic skeleton C 4 。
30 g of catalyst basic skeleton C 4 Adding into 262 ml toluene, leaching at 0deg.C for 40 seconds at 1000rpm with stirring, filtering, washing filter cake with cold toluene solvent for 3 times, repeating the leaching process for 3 times to remove hard template of block copolymer as much as possible, and marking the obtained product as catalyst precursor D 4 。
8 g of catalyst precursor D 4 Adding the mixture into 253 ml of cyclohexane, controlling the temperature to be 50 ℃, introducing inert gas for protection, adding 5 g of tetraisopropyl zirconate while stirring, continuously stirring and reacting for 48 hours, vacuum filtering to obtain a filter cake, and drying. The dry cake was then placed in 200 ml deionized water, stirred at 900rpm for 60 minutes, and vacuum filteredObtaining a hydrolysate filter cake, and drying the filter cake in vacuum for 12 hours to obtain powder E 4 。
Impregnating the powder E with 0.2M ammonium sulfate alcohol solution at room temperature and under 1200rpm stirring 4 Filtering in vacuum to obtain filter cake after 5 hr, vacuum drying at 120 deg.c for 8 hr, roasting in a box furnace at 600 deg.c for 4 hr, and burning polyether to obtain mesoporous MgO-macroporous ZrSO 5 "solid acid-base double function integrated catalyst".
Comparative example 1
Adding 56 g of nonionic amphiphilic block copolymer (48 g of P123 and 8 g of P103) into 52 g of deionized water, acidifying with nitric acid to pH=1.0, putting into a variable speed vortex mixer, uniformly mixing at 50 ℃, taking out, standing, self-assembling to form lyotropic liquid crystal micelles, and adding 14.2 g of Ca (NO 3 ) 2 ·4H 2 O and 185ml of ethyl orthosilicate are stirred at 1500rpm for 25 minutes to form a homogeneous basic matrix solution a of the catalyst 1 And (5) standby application.
Removing polymerization inhibitor in polymer monomer p-methylstyrene by conventional method, adding 168 g of purified monomer into 1370 ml of ultrapure water, introducing inert gas for protection, and dripping redox initiator ammonium persulfate and sodium bisulphite respectively under stirring at 1000rpm for 90 min, wherein the dripping amount of ammonium persulfate and sodium bisulphite is 3% and 0.7% of the mass of the polymer monomer, and the dripping process is divided into three stages, each stage is 30 min, and the temperature control of the three stages is 75 ℃, 80 ℃ and 85 ℃. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process of the white polymer colloid nanospheres after molding, the stirring speed is controlled at 200rpm, and the aging process is stirred for 12 hours. Then separating out polymer nanospheres by a high-speed refrigerated centrifuge at a speed of 15000rpm, washing for 5 times and vacuum drying at 80 ℃ to obtain the product, namely the poly-p-methylstyrene nanospheres b 1 。
150 g of solution a prepared as described above were mixed 1 And 75 grams of nanospheres b 1 Homogenizing under high speed stirring for 30 min, vacuum rotary evaporating to remove hydrolyzed small molecule product, and roomGelling and solidifying in warm air, aging for 48 hours to prepare the catalyst alkaline skeleton c 1 。
30 g of catalyst basic skeleton c 1 Adding into 250 ml of xylene, leaching at-5deg.C for 30 s with stirring rate of 1000rpm, filtering, washing filter cake with cold xylene solvent for 3 times, repeating the leaching process for 4 times to remove hard template of poly (p-methylstyrene) as much as possible, and marking the obtained product as catalyst precursor d 1 Vacuum drying at 120 deg.c for 8 hr, and roasting at 500 deg.c in a box furnace for 5 hr to burn polyether in the material and obtain mesoporous CaO-macroporous unmodified mesoporous solid base catalyst.
Comparative example 2
Adding 56 g of nonionic amphiphilic block copolymer (48 g of P123 and 8 g of P103) into 52 g of deionized water, acidifying with nitric acid to pH=1.0, putting into a variable speed vortex mixer, uniformly mixing at 50 ℃, taking out, standing, self-assembling to form lyotropic liquid crystal gel, adding 185ml of ethyl orthosilicate, and stirring at 1500rpm for 25 minutes to form uniform catalyst matrix solution a 2 And (5) standby application.
Removing polymerization inhibitor in polymer monomer p-methylstyrene by conventional method, adding 168 g of purified monomer into 1370 ml of ultrapure water, introducing inert gas for protection, and dripping redox initiator ammonium persulfate and sodium bisulphite respectively under stirring at 1000rpm for 90 min, wherein the dripping amount of ammonium persulfate and sodium bisulphite is 3% and 0.7% of the mass of the polymer monomer, and the dripping process is divided into three stages, each stage is 30 min, and the temperature control of the three stages is 75 ℃, 80 ℃ and 85 ℃. After the initiator is dripped, the stirring speed is controlled at 600rpm before the polymer colloid ball appears; in the aging process of the white polymer colloid nanospheres after molding, the stirring speed is controlled at 200rpm, and the aging process is stirred for 12 hours. Then separating out polymer nanospheres by a high-speed refrigerated centrifuge at a speed of 15000rpm, washing for 5 times and vacuum drying at 80 ℃ to obtain the product, namely the poly-p-methylstyrene nanospheres b 2 。
150 g of solution a prepared as described above were mixed 2 And 75 g NaRice ball b 2 Homogenizing under high speed stirring for 30 min, vacuum rotary evaporating to remove hydrolyzed small molecular product, gelatinizing and solidifying in air at room temperature, aging for 48 hr to obtain catalyst skeleton c 2 。
30 g of catalyst skeleton c 2 Adding into 250 ml of xylene, leaching at-5deg.C for 30 s with stirring rate of 1000rpm, filtering, washing filter cake with cold xylene solvent for 3 times, repeating the leaching process for 4 times to remove hard template of poly (p-methylstyrene) as much as possible, and marking the obtained product as catalyst precursor d 2 。
8 g of catalyst precursor d 2 Adding the mixture into 200 ml of hexane, controlling the temperature to be 80 ℃, introducing inert gas for protection, adding 4 g of tetrapropyl zirconate while stirring, continuously stirring for reaction for 24 hours, vacuum filtering to obtain a filter cake, and drying. Then putting the dry filter cake into 200 ml of deionized water, stirring for 60 minutes at 1000rpm, vacuum-pumping and filtering to obtain a hydrolysate filter cake, and vacuum-drying for 12 hours to obtain powder e 2 。
Impregnating the powder e with 0.3M ammonium sulfate alcohol solution at room temperature and stirring at 800rpm 2 Vacuum filtering to obtain filter cake after 3 hr, vacuum drying at 120deg.C for 8 hr, roasting at 500deg.C in box furnace for 5 hr, and burning polyether to obtain mesoporous unmodified macroporous ZrSO 5 "macroporous solid acid catalyst".
Elemental content was determined using an elemental analyzer (see table 2); the specific surface area and pore structure characteristics of the catalyst were tested by BET nitrogen adsorption and mercury intrusion (see FIGS. 3 and 4, table 1); XRD techniques were used to analyze the material for crystalline phases, kong Tezheng (see figures 1, 2); the acidic and basic site loadings were measured by titrimetric analysis techniques (see table 2).
As can be seen from the data in Table 1, the solid acid-base integrated catalyst prepared by the invention has a mesoporous and macroporous structure and a large specific surface area, so that the structural material has the basic condition of being a catalyst with excellent performance.
From the elemental analysis data and the active site loadings in Table 2, the catalyst of comparative example 1 only has basic sites and only catalyzes transesterification; the catalyst of comparative example 2 had only an acidic site and only catalyzed the esterification reaction.
The catalyst prepared in example 1 was tested and the results are shown in FIGS. 1-4.
The diffraction pattern of the small angle XRD diffraction pattern of FIG. 1 is clearly seen at diffraction angle 1.1 o The strongest diffraction peak nearby, which is characteristic of the (100) crystal face of the SBA-15 mesoporous material, shows that the SBA-15 mesoporous channel structure is successfully prepared in the catalyst.
As is clear from the wide angle XRD diffractogram of fig. 2, no characteristic peaks of crystalline phases of Ca, zr compounds appear, indicating that they exist in highly dispersed amorphous state in the synthesized catalyst material.
The pore size distribution was made by BET nitrogen adsorption as in FIG. 3, and it can be seen that the mesoporous pore size data is consistent with the results in Table 1, which is typical of the SBA-15 mesoporous pore size. The mercury intrusion method mainly measures the macropore parameters in the material, and the related results are shown in table 1. These data further confirm that mesoporous and macroporous structures are indeed produced in the catalyst material.
N as shown in FIG. 4 was also produced by BET nitrogen adsorption 2 The physical adsorption and desorption isotherm is an IV type adsorption and desorption isotherm with H1 type hysteresis loop, which is a typical characteristic of SBA-15 mesoporous materials with relatively narrow pore size distribution, and further proves that a mesoporous structure is truly prepared in the catalyst material.
Catalyst performance test:
the essential compositions and main parameters of cottonseed oil I (low acid value sample), cottonseed oil II (high acid value sample, cottonseed oil I and oleic acid uniformly mixed in a mass ratio of 5:1) used in the following examples are shown in Table 3.
Example 5
60g of cottonseed oil I (acid value: 1.0) and 605ml of isooctyl alcohol and 8.4g of catalyst (catalyst prepared in example 1) were added to a reaction pilot plant, the temperature was programmed to 70 ℃, the mixture was magnetically stirred, the catalyst was removed by suction filtration after 6 hours of reaction, the filtrate was allowed to stand and separate, the upper layer was mainly composed of isooctyl fatty acid ester and isooctyl alcohol, and the lower layer was mainly composed of glycerol and isooctyl alcohol. And (3) after molecular distillation is carried out on the upper oil phase to recover isooctyl alcohol, determining an acid value and an ester exchange conversion rate (specific data are shown in table 4), and sequentially carrying out procedures such as adsorption decoloration, filtration and the like to obtain a refined fatty acid isooctyl ester product.
Comparative example 3
The catalyst was the catalyst prepared in comparative example 1, and the other steps were the same as in example 5.
Comparative example 4
The catalyst was the catalyst prepared in comparative example 2, and the other steps were the same as in example 5.
Example 6
60g of cottonseed oil II (namely 50g of cottonseed oil I and 10g of oleic acid are uniformly mixed) is added into a reaction rectification small test device, the mixture is uniformly stirred and mixed (the acid value is 33.26), 605ml of isooctyl alcohol and 8.4g of catalyst (the catalyst prepared in the example 1) are added, the temperature is programmed to 95 ℃, the magnetic stirring is carried out, a certain degree of negative pressure is maintained in a reaction rectification kettle, water generated by the esterification reaction is distilled out in time, after the reaction rectification is carried out for 6 hours, the catalyst is removed by suction filtration, the filtrate is kept stand for layering, the upper layer is mainly fatty acid isooctyl ester, isooctyl alcohol and trace oleic acid, and the lower layer is mainly glycerol, isooctyl alcohol and trace water. After the isooctyl alcohol is recovered by molecular distillation of the upper oil phase, the acid value, the oleic acid conversion rate and the transesterification conversion rate are measured (specific data are shown in table 4), and the refined fatty acid isooctyl ester product can be obtained by the steps of alkali refining (removing unreacted oleic acid), water washing, adsorption decoloration, filtration, water removal and the like.
Comparative example 5
The catalyst was the catalyst prepared in comparative example 1, and the other steps were the same as in example 6.
Comparative example 6
The catalyst was the catalyst prepared in comparative example 2, and the other steps were the same as in example 6.
From the data in table 4, the following conclusions can be drawn:
(1) When the cottonseed oil is the low acid value raw material I, the catalyst prepared in comparative example 1 (only basic sites, no acidic sites) has the catalytic performance (comparative example 3) as compared with the mesoporous CaO-macroporous ZrSO prepared in example 1 5 The catalytic performance (example 5) of the solid acid-base bifunctional integrated catalyst is equivalent, the transesterification conversion rate of the cottonseed oil is higher than 97%, the acid value of the crude fatty acid ester prepared by the reaction is very low, namely about 0.05mgKOH/g, and the catalytic performance of the solid acid-base bifunctional integrated catalyst is proved to be very excellent; the catalyst prepared in comparative example 2 (only acidic sites, no basic sites) had poor catalytic performance on the transesterification of cottonseed oil, and the transesterification conversion was only 8%. This indicates that it is the basic site that has strong catalytic activity for the transesterification of cottonseed oil.
(2) When the cottonseed oil is the high acid value raw material II, the catalytic performance of the catalyst prepared in the example 1 on the transesterification of the cottonseed oil (example 6) is equivalent to that of the example 5, the conversion rate is only slightly reduced from 97.1% to 96.8%, and the conversion rate of the contained oleic acid in the esterification reaction is as high as 96.2%, because the catalyst prepared in the example 1 is a solid acid-base integrated catalyst, wherein the alkaline site catalyzes the transesterification, the acidic site catalyzes the esterification reaction of the free fatty acid, and the existence of the free fatty acid does not affect the catalytic activity of the catalyst on the transesterification of the cottonseed oil, and the reason is that: the prepared catalyst has the advantages that acid and alkali active sites are separated in space positions and are respectively distributed in macropores on the surface and mesopores in the material, the high acid value cottonseed oil is contacted with the acid sites in the macropores, free fatty acid is basically esterified at the sites, then is diffused into a mesoporous structure through a channel between the macropores and the mesopores, transesterification of the cottonseed oil occurs at the sites, and the time sequence of the reaction brought by the space sequence is a key place for avoiding poisoning and inactivation of the active alkaline sites caused by the free fatty acid; whereas the catalyst prepared in comparative example 1 (only basic site, no acidic site) had a greatly reduced catalytic performance for transesterification of high acid value cottonseed oil (comparative example 5), the transesterification conversion was only 10.6%, which is far inferior to the transesterification conversion of low acid value cottonseed oil by 97.4%, which suggests that on a catalyst lacking acidic sites, a large amount of free fatty acids could not be esterified, thus covering the active basic site to inactivate the toxicity therein; similar to comparative example 4, the catalyst prepared in comparative example 2 (only acid site, no alkaline site) has poor catalytic performance on transesterification of high acid value cottonseed oil (comparative example 6), the transesterification conversion rate is only 7.6%, but the catalyst has good catalytic performance on esterification of free fatty acid, and the esterification conversion rate of oleic acid can reach 96.5%.
Example 7
Under the experimental conditions of example 5, the characteristic of the repeated utilization of the solid acid-base bifunctional integrated catalyst is examined, the catalyst separated by suction filtration each time is dried in an oven at 120 ℃ for 12 hours in vacuum and then is used for catalyzing the next transesterification reaction, the catalyst is repeatedly utilized for 8 times, and the transesterification conversion rate of the cottonseed oil is reduced to 72.3 percent.
Example 8
Under the experimental conditions of example 5, the characteristic of the repeated utilization of the solid acid-base bifunctional integrated catalyst is examined, the catalyst separated by suction filtration is washed 3 times by methanol each time, is dried in an oven at 120 ℃ for 12 hours in vacuum and then is used for catalyzing the next transesterification reaction, and is recycled 8 times, so that the transesterification conversion rate of the cottonseed oil is reduced to 92.8%. The catalyst was placed in a box furnace at 400 ℃ and heat treated with air for 30 minutes, taken out and naturally cooled to room temperature, and used again in the experiment of example 5, the transesterification conversion of cottonseed oil was raised back to 96.8%.
Example 9
Under the experimental condition of example 6, the characteristic of the performance attenuation of the solid acid-base bifunctional integrated catalyst for recycling is examined, the catalyst separated by suction filtration each time is dried in an oven at 120 ℃ for 12 hours in vacuum and then is used for catalyzing the next reaction, the catalyst is recycled for 8 times, and the transesterification conversion rate and the oleic acid conversion rate of the cotton seed oil are respectively reduced to 71.4 percent and 70.6 percent.
Example 10
Under the experimental condition of example 6, the characteristic of the performance attenuation of the solid acid-base bifunctional integrated catalyst for recycling is examined, the catalyst separated by suction filtration is washed 3 times by methanol each time, is dried in vacuum in an oven at 120 ℃ for 12 hours and then is used for catalyzing the next reaction, and is recycled 8 times, and the transesterification conversion rate and the oleic acid conversion rate of the cotton seed oil are respectively reduced to 90.5% and 89.4%. The catalyst was placed in a box furnace at 400 ℃ and heat-treated with air for 30 minutes, taken out and naturally cooled to room temperature, and used again in the experiment of example 6, the conversion rate of the cottonseed oil transesterification and the conversion rate of the oleic acid were respectively raised to 95.7% and 95.1%.
The experimental results of the above examples 7-10 show that the solid acid-base integrated catalyst prepared by the invention has slow performance decay in the recycling process, and better catalytic performance retention can be obtained if the treatment process of 'washing with alcohol solvent for many times' is adopted after each separation; if the medium-temperature air heat treatment is performed once after 8 times of recycling, the catalytic performance can be almost restored to the level of the fresh catalyst.
Example 11
Blending the refined fatty acid isooctyl ester product prepared in the example 6 with frozen refined cottonseed oil according to a proportion, respectively adding 0.5% of antioxidant tert-butylhydroquinone, 0.3% of metal passivating agent benzotriazole and 1% of narrow molecular weight copolymer composite pour point depressant to obtain a cottonseed oil-based transformer insulating oil product, and testing the object, chemical, thermal and electrical properties of the product according to international/domestic/industry standards, wherein relevant technical parameters are shown in Table 5.
As can be seen from the data in Table 5, the cottonseed oil-based transformer insulating oil prepared by the invention has excellent performance, all indexes reach the specified range of international/domestic/industrial technical standards, especially the breakdown voltage (2.5 mm) can reach 68kV, and the electrical performance is excellent; the flash point is 280 ℃, the ignition point is 313 ℃ which is far higher than that of mineral insulating oil, the fireproof performance is excellent, and the use safety performance is high; the pour point reaches-35 ℃, and can be used for power supply and transformation systems in northeast, northwest, qinghai-Tibet plateau and other places with harsh low-temperature performance requirements.
In conclusion, the solid acid-base bifunctional integrated catalyst prepared by the invention has a macroporous and mesoporous hierarchical structure, active acid and alkali sites are separated in the pore canal structure of the catalyst and are respectively positioned in the macropores and the mesopores, so that the problem of catalyst poisoning and deactivation caused by the excessively high acid value of raw materials (high content of free fatty acid) can be effectively prevented in the one-pot transesterification process, and the limit requirement on the acid value of the raw materials is reduced.
Claims (10)
1. The preparation method of the solid acid-base catalyst for producing the transformer insulating oil is characterized by comprising the following steps of:
(1) Construction of catalyst structure framework
a. Preparation of basic catalyst matrix
Firstly adding an amphiphilic block copolymer into deionized water, adding acid for acidification, uniformly mixing, standing, self-assembling to form a lyotropic liquid crystal micelle, then adding metal nitrate and silicate, and stirring to obtain a catalyst alkaline matrix solution A;
b. preparation of monodisperse polymer colloid nanospheres used as macroporous hard templates
Under the protection of inert gas and stirring conditions, dropwise adding an initiator into the polymer monomer and ultrapure water for reaction to obtain white polymer colloid nanospheres, washing the white polymer colloid nanospheres, and drying in vacuum to obtain nanospheres B;
or under the condition of inert gas protection and stirring, dropwise adding an initiator into a polymer monomer, a coupling monomer, an emulsifier and ultrapure water for reaction to obtain white polymer colloid nanospheres, washing the white polymer colloid nanospheres, and drying in vacuum to obtain nanospheres B;
c. blending and gelling of catalyst alkaline matrix and macroporous template
Mixing the catalyst alkaline matrix solution A and the nanospheres B, stirring, homogenizing and aging to obtain a catalyst alkaline framework C;
(2) Leaching of macroporous template in catalyst framework and loading of solid super acid active site
a. Leaching of macroporous templates in catalyst frameworks
Adding the catalyst alkaline framework C into a good solvent of a polymer hard template, stirring, leaching, filtering and washing a filter cake to obtain a catalyst precursor D after the hard template is removed;
b. loading of acidic active sites in catalysts
Adding the catalyst precursor D into an organic solvent, adding an organic metal compound for reaction under the conditions of inert gas protection and stirring, vacuum filtering to obtain a filter cake, and drying to obtain a dry filter cake;
hydrolyzing the dry filter cake to obtain a hydrolysate filter cake, and drying in vacuum to obtain powder E;
under the condition of room temperature and stirring, the powder E is immersed and treated by an alcohol solution of ammonium sulfate, a filter cake is obtained by vacuum suction filtration, and a solid acid-base catalyst for producing the transformer insulating oil is obtained by vacuum drying and roasting.
2. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the amphiphilic block copolymer in the step (1) a is polyether with a structure of PEO-PPO-PEO, the acid is one of inorganic acid and organic acid, the acidification is carried out to pH=0-3, the mixing temperature is room temperature-60 ℃, and the mass ratio of deionized water to amphiphilic block copolymer is 3:2-4.5.
3. The preparation method of the solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein in the step (1), the metal nitrate is one or more of alkaline earth metal nitrate, transition metal nitrate or rare earth metal nitrate, and the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate; the stirring speed is 1000-2000rpm, the stirring time is 15-30 minutes, and the mol ratio of the amphiphilic block copolymer to the metal nitrate to the silicate is 1:5-8:60-110.
4. The preparation method of the solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the polymer monomer in the step (1) is one or more of styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene, p-isobutyl styrene and p-tert-butyl styrene; the coupling monomer is one of maleic anhydride or acrylic ester; the emulsifier is alkylphenol ethoxylate OP-10 or sodium dodecyl sulfate; the initiator is one of a single initiator or a composite initiator; wherein the single initiator is one of potassium persulfate, ammonium persulfate or hydrogen peroxide, and the composite initiator is one of potassium persulfate, ammonium persulfate or hydrogen peroxide and one or more of sodium sulfite, sodium bisulphite, sodium dithionate or L-ascorbic acid; the mass ratio of the polymer monomer to the ultrapure water is 1:6-10.
5. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the reaction temperature in step (1) b is 75-85 ℃, the washing times are 3-6 times, and the vacuum drying temperature is 60-120 ℃.
6. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the stirring time in the step (1) c is 15-30 minutes, the aging time is 24-72 hours, and the mass ratio of the catalyst alkaline matrix solution A to the nanospheres B is 3-4:2.
7. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the good solvent in the step (2) a is one of toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetone, dichloromethane or chloroform; the leaching temperature is-5 to 0 ℃ and the leaching time is 20 to 40 seconds; the washing is carried out by adopting cold good solvent, the washing times are 2-3 times, the mass ratio of the catalyst alkaline framework C to the good solvent is 1:6.5-9, and the stirring speed is 800-1200rpm.
8. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the organic solvent in the step (2) is one of cyclohexane, hexane, carbon tetrachloride, propanol, isopropanol, tetrahydrofuran, ethyl acetate, chloroform, methyl ethyl ketone or acetone; the organic metal compound is one or more of organic titanium compound, organic zirconium compound, organic hafnium compound, organic iron compound or organic tin compound; the organic titanium compound is one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate or tetrabutyl titanate, the organic zirconium compound is one of tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate or tetrabutyl zirconate, the organic hafnium compound is one of tetraethyl hafnate, tetrapropyl hafnate, tetraisopropyl hafnate or tetrabutyl hafnate, the organic iron compound is one of ferric ethanol, ferric n-propanol, ferric isopropanol or ferric n-butanol, and the organic tin compound is one of tin ethanol, tin n-propanol, tin isopropanol or tin n-butanol; the mass ratio of the catalyst precursor D to the organic solvent is 1:14-30, and the mass ratio of the catalyst precursor D to the organic metal compound is 1-4:1.
9. The method for preparing a solid acid-base catalyst for producing transformer insulating oil according to claim 1, wherein the reaction temperature in step (2) b is 50-80 ℃, the reaction time is 24-48 hours, the impregnation time is 2-6 hours, the calcination temperature is 400-700 ℃, the calcination time is 4-6 hours, and the concentration of the alcohol solution of ammonium sulfate is 0.1-0.4mol/L.
10. The use of a catalyst prepared by the method for preparing a solid acid-base catalyst for producing transformer insulating oil according to any one of claims 1 to 9, characterized in that the catalyst is used for producing transformer insulating oil by transesterification of vegetable oil.
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| CN202310042526.5A CN116037164B (en) | 2023-01-28 | 2023-01-28 | Preparation method and application of solid acid-base catalyst for producing transformer insulating oil |
| PCT/CN2024/070552 WO2024156253A1 (en) | 2023-01-28 | 2024-01-04 | Solid acid-base catalyst for producing transformer insulating oil as well as preparation method therefor and use thereof |
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| WO2024156253A1 (en) * | 2023-01-28 | 2024-08-02 | 山东理工大学 | Solid acid-base catalyst for producing transformer insulating oil as well as preparation method therefor and use thereof |
| CN119500218A (en) * | 2024-11-01 | 2025-02-25 | 华南理工大学 | A preparation method and application of boron-doped carbon-based iron single-atom material by two-step calcination |
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