CN113289644A - Solid acid material applied to catalytic synthesis of biodiesel and preparation method thereof - Google Patents
Solid acid material applied to catalytic synthesis of biodiesel and preparation method thereof Download PDFInfo
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- CN113289644A CN113289644A CN202110591586.3A CN202110591586A CN113289644A CN 113289644 A CN113289644 A CN 113289644A CN 202110591586 A CN202110591586 A CN 202110591586A CN 113289644 A CN113289644 A CN 113289644A
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000011973 solid acid Substances 0.000 title claims abstract description 50
- 239000003225 biodiesel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 5
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 claims description 4
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 4
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 4
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- APTVNWGLSRAOFJ-UHFFFAOYSA-M dimethyl(dioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)CCCCCCCC APTVNWGLSRAOFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 2
- NLOQZPHAWQDLQW-UHFFFAOYSA-J zirconium(4+);disulfate;tetrahydrate Chemical compound O.O.O.O.[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NLOQZPHAWQDLQW-UHFFFAOYSA-J 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 55
- 235000012424 soybean oil Nutrition 0.000 abstract description 23
- 239000003549 soybean oil Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000005809 transesterification reaction Methods 0.000 abstract description 12
- 235000019441 ethanol Nutrition 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 2
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- BNGKLHOXDJYQPB-UHFFFAOYSA-M ethanol hexadecyl(trimethyl)azanium chloride Chemical compound C(C)O.[Cl-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C BNGKLHOXDJYQPB-UHFFFAOYSA-M 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 2
- 229940117972 triolein Drugs 0.000 description 2
- YFVXLROHJBSEDW-UHFFFAOYSA-N 4-[(4-nitrophenyl)diazenyl]-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1N=NC(C=C1)=CC=C1NC1=CC=CC=C1 YFVXLROHJBSEDW-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- LJQSESUEJXAKBR-UHFFFAOYSA-J zirconium(4+) tetrachloride octahydrate Chemical compound O.O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] LJQSESUEJXAKBR-UHFFFAOYSA-J 0.000 description 1
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- 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
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a solid acid material applied to catalytic synthesis of biodiesel and a preparation method thereof, and particularly relates to a method for preparing a solid acid material by transferring a solution into a hydrothermal kettle for treatment to obtain a pre-crystallized product, and adjusting the pH to 9 by ammonia water; transferring the product to a hydrothermal kettle for further crystallization, washing the product obtained by secondary crystallization to be neutral by ethanol, drying the product in a drying oven, removing the template agent, dipping the roasted product in a sulfuric acid solution, performing suction filtration on the obtained product, roasting the dried product of the filter cake to obtain the acid catalytic material, wherein the use amount of the raw materials meets the requirements of a zirconium source to organic amine: organic ammonium salt: tin source: the molar ratio of the absolute ethyl alcohol = 900-1820: 125-270: 250-400: 25-140: 100000. The solid acid material prepared by the invention can be used for catalyzing the reaction of soybean oil and methanol for preparing biodiesel through transesterification, and can show extremely high transesterification activity of soybean oil and methanol and biodiesel selectivity; the preparation process is simple and easy to implement, and the reproduction rate is high.
Description
Technical Field
The invention belongs to the fields of physical chemistry and material chemistry, and discloses a solid acid material applied to catalytic synthesis of biodiesel and a preparation method thereof.
Background
Since the 21 st century, energy crisis and environmental pollution have become major issues facing all mankind. The contradiction between supply and demand of petroleum is increasingly prominent, and the research of new alternative energy becomes urgent. Particularly for China, the demand of petroleum is increased rapidly along with rapid development of economy in recent years, and the supply gap is larger and larger. Under the background, various countries have a pace of accelerating the development of fossil fuel alternative energy, and the biodiesel receives attention from various countries due to the excellent environmental protection performance of the biodiesel. The main component of the biodiesel is fatty acid methyl ester with different chain lengths, and the biodiesel is generally prepared by ester exchange reaction of animal and vegetable oil and methanol. The production method of biodiesel can be divided into acid catalysis and base catalysis according to the kind of the catalyst used. Although the basic catalyst can catalyze the transesterification under mild conditions, saponification of the oil and fat is easily initiated, and the basic catalyst is easily deactivated by water and free fatty acids in the oil and fat. The acidic catalyst can catalyze the grease with high acid value, and can catalyze the ester exchange reaction and the esterification reaction to be carried out simultaneously, thereby improving the yield of the biodiesel. Therefore, the application range of preparing the biodiesel by acid-catalyzed transesterification is wider. Zirconium oxide is used as a super acidic catalyst, and can efficiently catalyze esterification reaction and ester exchange reaction.
The studies of Kiss and the like show that sulfated zirconia has good activity and selectivity in the esterification reaction of alcohol and free fatty acid. This lays a theoretical foundation for the preparation of biodiesel with sulfated zirconia as a solid acid catalyst. Garcia can obtain 100% of soybean oil conversion rate at 120 ℃ by using sulfated zirconia prepared by a solvent-free method, but the application of the sulfated zirconia is severely limited by the defects of quick inactivation, loss of sulfur and the like. Sivakumar introduces elements such as iron and manganese in the process of synthesizing sulfated zirconia. The synthesized material has the biodiesel yield of more than 90% after 5 times of catalysis in the transesterification catalysis process of animal fat and methanol, and shows good catalytic activity and stability.
Disclosure of Invention
In view of the above circumstances, the present invention aims to: the solid acid material is applied to catalytic synthesis of biodiesel and the preparation method thereof, and can be used for preparing biodiesel by catalyzing transesterification of soybean oil and methanol with high conversion rate and high selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the solid acid material is prepared from a zirconium source, a tin source, organic amine, organic ammonium salt, ammonia water, sulfuric acid, absolute ethyl alcohol and deionized water, wherein the dosage of the raw materials meets the requirement that the ratio of the zirconium source to the organic amine is as follows: organic ammonium salt: tin source: the molar ratio of the absolute ethyl alcohol = 900-1820: 125-270: 250-400: 25-140: 100000.
In the solid acid catalytic material, the raw material zirconium source is any one or a mixture of more of tetrahydrate zirconium sulfate, normal butanol zirconium, pentahydrate zirconium nitrate and octahydrate zirconium oxychloride.
The tin source is any one of tin tetrabromide, anhydrous tin chloride and pentahydrate tin chloride.
The organic amine is any one of triethanolamine or triisopropanolamine.
The organic ammonium salt is any one of hexadecyl trimethyl ammonium chloride, dioctyldimethyl ammonium bromide, didecyl dimethyl ammonium chloride or didecyl dimethyl ammonium bromide.
The solid acid catalytic material has a nano-stacking mesoporous structure, larger specific surface area and pore volume,the mesoporous aperture is adjustable, the mesoporous aperture is 2-30 nm, and the specific surface area is 110-190 m2Per gram, pore volume 0.16-0.3 cm3Adjustable in the range of/g.
Furthermore, the preparation method of the solid acid material for catalyzing and synthesizing the biodiesel is specifically prepared according to the following steps:
(1) according to the ratio of zirconium source to organic amine: organic ammonium salt: tin source: absolute ethyl alcohol = 900-1820: 125-270: 250-400: 25-140: 100000, and the zirconium source, the tin source, the organic amine and the organic ammonium salt are completely dissolved into the absolute ethyl alcohol in sequence to obtain a clear solution;
(2) placing the clear solution in a hydrothermal kettle at the temperature of 60-90 ℃ for pre-crystallization treatment for 0.5-3 h to obtain a pre-crystallization product;
(3) dropwise adding ammonia water into the pre-crystallized product to adjust the pH = 9;
(4) the treated product is crystallized again in a hydrothermal kettle at the temperature of 100-140 ℃ for 24-48 h;
(5) washing the product after the secondary crystallization by using absolute ethyl alcohol until the product is neutral, and drying the washed product at the temperature of 60-80 ℃;
(6) drying the obtained product, roasting at 300-350 ℃, and removing the organic template;
(7) dipping each 1g of product without the organic template agent by using 10-20 ml of sulfuric acid solution with the concentration of 0.5-2 mol/L for 0.5-3 h;
(8) after the solution after impregnation is subjected to suction filtration, drying a filter cake at 100-120 ℃;
(9) roasting the dried product at 450-600 ℃ for 3-5 h to obtain SO4 2-/SnO2-ZrO2A solid acid catalytic material.
SO given as described in the invention4 2-/SnO2-ZrO2In the preparation method of the solid acid catalytic material, under a synthesis system taking ethanol as a solvent, organic ammonium salt forms mutually-crosslinked network-structure micelles in the ethanol, and forms an aggregated precursor solution with a zirconium source and a tin source chelated by organic amine. Pre-crystallizing at a certain temperature, wherein part of chelated zirconium source and tin source pass through slowlyTo form the corresponding hydroxy compound. After the pre-crystallization is finished, more hydroxyl groups are introduced by dropwise adding ammonia water, and the balance of hydrolysis and agglomeration is achieved by controlling the speed of dropwise adding ammonia water. In alkaline solution, the zirconium source is gradually hydrolyzed and polymerized to form a combination of organic ammonium salt template and zirconium and tin hydrolysate. The organic template agent is removed through the high-temperature roasting process, and mesoporous channels among particles are formed at the position where the template agent exists. During the sulfuric acid impregnation process, sulfuric acid is adsorbed on SnO2-ZrO2Of (2) is provided. Through a further roasting process, SO with high specific surface area, large pore diameter and pore volume and high dispersion of tin and sulfur is prepared4 2-/SnO2-ZrO2A solid acid catalytic material. In the process, the specific surface area, the pore volume and the mesoporous aperture of the obtained material are regulated and controlled by regulating and controlling the introduction types, crystallization temperature and roasting temperature of the organic ammonium salt ionic surfactant and the organic amine and the introduction amount of a tin source and a sulfur source; the crystallization degree of the zirconia is adjusted by optimizing the roasting conditions (including temperature and heating rate), so as to regulate and control the crystal phase structure and the crystal grain size of the obtained zirconia material, and the introduction amount of the tin and the sulfur in the zirconia is regulated and controlled by regulating and controlling the addition amount of the tin and the sulfur.
The invention has the beneficial effects that: SO given4 2-/SnO2-ZrO2The solid acid catalytic material can be used as a catalyst for catalyzing the transesterification of soybean oil and methanol to prepare biodiesel; it can show very high soybean oil and methanol ester exchange activity and biodiesel selectivity. Under the conditions that the molar ratio of methanol to triolein is 20:1 at 140 ℃, the reaction lasts for 5 hours, the dosage of the catalyst is 3 percent of the mass of the soybean oil, the conversion rate of the soybean oil is not lower than 99 percent, and the content of the biodiesel in the product is not lower than 97 percent; in addition, SO prepared according to the invention4 2-/SnO2-ZrO2The solid acid catalytic material has excellent on-site performance, and the structure, texture and catalytic performance of the transesterification reaction of soybean oil and methanol are not changed after the solid acid catalytic material is repeatedly used for 7 times; the preparation method has simple and easy process and high reproduction rate.
Drawings
FIG. 1 is SO4 2-/SnO2-ZrO2XRD spectrogram of the solid acid catalytic material;
FIG. 2 is SO4 2-/SnO2-ZrO2SEM photograph of solid acid catalytic material;
FIG. 3 is SO4 2-/SnO2-ZrO2High resolution TEM pictures of solid acid catalytic materials;
FIG. 4 is SO4 2-/SnO2-ZrO2N of solid acid catalytic material2Adsorption-desorption isotherms;
FIG. 5 is SO4 2-/SnO2-ZrO2N of solid acid catalytic material2Pore size distribution curve;
FIG. 6 is SO4 2-/SnO2-ZrO2NH of solid acid catalytic material3-a TPD map;
FIG. 7 is SO4 2-/SnO2-ZrO2The solid acid catalytic material catalyzes the conversion rate of soybean oil and the selectivity of biodiesel in different reaction time in the reaction of the soybean oil and methanol;
FIG. 8 is SO4 2-/SnO2—ZrO2And (3) a trend graph of the catalytic performance of the solid acid catalytic material along with the change of the catalytic reaction times.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and do not limit the scope of the present invention. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes: (1) under the condition of strong stirring at 32 ℃, 4g of zirconium nitrate pentahydrate, 0.2g of stannic chloride pentahydrate and 0.3g of triethanolamine are dissolved in 50ml of absolute ethyl alcohol in sequence to obtain a clear solution, which is counted as solution A; 0.8g of dioctadecyldimethylammonium chloride is dissolved in 10ml of absolute ethyl alcohol and is counted as solution B; slowly adding the ethanol solution of the dioctadecyldimethyl ammonium chloride into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 70 ℃ for 4 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating for 48 hours at 100 ℃ to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying for 24 hours at the temperature of 60 ℃;
(6) heating the dried sample to 300 ℃ at the heating rate of 1 ℃/min, and roasting for 5h to remove the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample for removing the template agent by using 10ml of sulfuric acid with the concentration of 1.5mol/L for 0.5 h;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 100 ℃ for 18 hours;
(9) heating the dried impregnated sample to 550 ℃ at the heating rate of 1 ℃/min and roasting for 3h to obtain SO4 2-/SnO2-ZrO2A solid acid catalytic material.
Example 2
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes:
(1) under strong stirring at 32 ℃, dissolving 6g of zirconium chloride octahydrate, 0.07g of anhydrous stannic chloride and 0.25g of triisopropanolamine in 50ml of anhydrous ethanol in sequence to obtain a clear solution, namely a solution A; dissolving 1.1g of didecyl dimethyl ammonium chloride in 10ml of absolute ethyl alcohol to obtain a solution B; slowly adding the ethanol solution of the didecyl dimethyl ammonium chloride into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 80 ℃ for 4 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating at 120 ℃ for 24 hours to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying at 70 ℃ for 12 h;
(6) heating the dried sample to 300 ℃ at the heating rate of 1 ℃/min, and roasting for 5h to remove the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample without the organic template agent for 1h by using 15ml of sulfuric acid with the concentration of 1 mol/L;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 110 ℃ for 12 hours;
(9) heating the dried impregnated sample to 300 ℃ at the heating rate of 1 ℃/min and roasting for 5h to prepare SO4 2-/SnO2-ZrO2A solid acid catalytic material.
Example 3
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes:
(1) under strong stirring at 32 ℃, dissolving 5g of zirconium sulfate tetrahydrate, 0.11g of tin tetrabromide and 0.3g of triisopropanolamine in 50ml of absolute ethyl alcohol in sequence to obtain a clear solution, namely a solution A; dissolving 1.2g of hexadecyl trimethyl ammonium chloride in 10ml of absolute ethyl alcohol to obtain a solution B; slowly adding a cetyl trimethyl ammonium chloride ethanol solution into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 90 ℃ for 3 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating at 140 ℃ for 24 hours to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying at 80 ℃ for 12 h;
(6) heating the dried sample to 300 ℃ at the heating rate of 1 ℃/min, and roasting for 5h to remove the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample for removing the organic template for 3 hours by using 20ml of sulfuric acid with the concentration of 0.5 mol/L;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 120 ℃ for 6 hours;
(9) heating the dried impregnated sample to 500 ℃ at the heating rate of 1 ℃/min and roasting for 4h to prepare SO4 2-/SnO2-ZrO2A solid acid catalytic material.
Example 4
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes:
(1) under strong stirring at 32 ℃, dissolving 6g of zirconium nitrate pentahydrate, 0.5g of stannic chloride pentahydrate and 0.2g of triethanolamine in 50ml of absolute ethanol in sequence to obtain a clear solution, and calculating the clear solution as a solution A; dissolving 1g of hexadecyl trimethyl ammonium chloride in 10ml of absolute ethyl alcohol to obtain a solution B; slowly adding a cetyl trimethyl ammonium chloride ethanol solution into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 80 ℃ for 4 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating at 120 ℃ for 36 hours to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying for 24 hours at the temperature of 80 ℃;
(6) heating the dried sample to 300 ℃ at the heating rate of 1 ℃/min, roasting for 6h, and removing the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample without the organic template agent for 2h by using 10ml of sulfuric acid with the concentration of 2 mol/L;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 100 ℃ for 12 hours;
(9) heating the dried impregnated sample to 450 ℃ at the heating rate of 1 ℃/min and roasting for 5h to prepare SO4 2-/SnO2-ZrO2A solid acid catalytic material.
Example 5
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes:
(1) under strong stirring at 32 ℃, dissolving 5g of zirconium oxychloride octahydrate, 0.21g of anhydrous stannic chloride and 0.4g of triethanolamine in 50ml of anhydrous ethanol in sequence to obtain a clear solution, wherein the clear solution is counted as a solution A; dissolving 1.25g of dioctadecyldimethylammonium bromide in 10ml of absolute ethanol to obtain solution B; slowly adding the ethanol solution of dioctadecyldimethylammonium bromide into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 80 ℃ for 4 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating at 120 ℃ for 24 hours to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying at 60 ℃ for 12 h;
(6) heating the dried sample to 350 ℃ at the heating rate of 1 ℃/min, roasting for 3h, and removing the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample subjected to organic template removal by using 15ml of sulfuric acid with the concentration of 1mol/L for 3 hours;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 120 ℃ for 6 hours;
(9) heating the dried impregnated sample to 500 ℃ at the heating rate of 1 ℃/min and roasting for 4h to prepare SO4 2-/SnO2-ZrO2A solid acid catalytic material.
Example 6
A preparation method of a solid acid material applied to catalytic synthesis of biodiesel comprises the following specific preparation processes:
(1) dissolving 4g of n-butyl zirconium, 0.36g of tin tetrabromide and 0.4g of triisopropanolamine in 50ml of absolute ethyl alcohol in sequence under strong stirring at 32 ℃ to obtain a clear solution, namely a solution A; dissolving 1.25g of didecyl dimethyl ammonium bromide in 10ml of absolute ethyl alcohol to obtain a solution B; slowly adding the ethanol solution of didecyl dimethyl ammonium bromide into the solution A;
(2) transferring the mixed solution into a hydrothermal kettle with a 100ml polytetrafluoroethylene lining, and treating at 70 ℃ for 4 hours to obtain a pre-crystallized product;
(3) transferring the pre-crystallized product to a glass beaker, and slowly dropwise adding ammonia water to adjust the pH =9 under the stirring condition;
(4) transferring the product into a hydrothermal kettle with 100ml of polytetrafluoroethylene lining, and treating at 140 ℃ for 24 hours to obtain a secondary crystallization product;
(5) washing the secondary crystallization product to be neutral by using absolute ethyl alcohol, and drying at 60 ℃ for 12 h;
(6) heating the dried sample to 330 ℃ at the heating rate of 1 ℃/min, and roasting for 5h to remove the organic template agent existing in the mesoporous pore canal;
(7) dipping each 1g of sample for removing the organic template for 0.5h by using 20ml of sulfuric acid with the concentration of 0.5 mol/L;
(8) after the impregnation is finished, filtering out redundant sulfuric acid solution by reduced pressure suction filtration, and drying the obtained filter cake at 100 ℃ for 12 hours;
(9) heating the dried impregnated sample to 550 ℃ at the heating rate of 1 ℃/min and roasting for 5h to obtain SO4 2-/SnO2-ZrO2A solid acid catalytic material.
As shown in FIG. 1, is SO4 2-/SnO2-ZrO2The XRD spectrum of the solid acid catalytic material shows that the sample has distinct diffraction peaks at 2 θ =30.2 °, 35.3 °, 50.3 °, 60.2 ° and 62.8 °, demonstrating that zirconia is a tetragonal structure. Meanwhile, no characteristic diffraction peak of the tin oxide is found, which indicates that the tin oxide is uniformly dispersed in the zirconium oxide; in addition, the size of the zirconium oxide crystal grains is calculated by the Sherle formula to be about 10 nm.
As shown in FIGS. 2 and 3, is SO4 2-/SnO2-ZrO2The SEM photograph and the high-resolution TEM photograph of the solid acid catalytic material show that the material has a nano-stacking structure, and the high-resolution TEM photograph (B) shows that the grain size of the material is about 10nm, which is consistent with the XRD calculation result.
N from the material of FIG. 42The adsorption-desorption isotherms show that the sample exhibits a typical type iv adsorption isotherm and a hysteresis loop of type H3, indicating that the solid material contains irregular channels with packed particles.
As can be seen from the pore size distribution curve of fig. 5, the pore channel distribution of the sample is broad. The specific surface area and the pore volume of the sample were 190m, respectively2G and 0.3cm3(ii)/g, the average mesoporous diameter is 4.9 nm.
As shown in FIG. 6, it can be seen that the ammonia desorption peak at 200-300 ℃ corresponds to the weak acid sites in the material, the ammonia desorption peak at 300-450 ℃ corresponds to the medium acid sites in the material, and the ammonia desorption peak at 450-600 ℃ corresponds to the strong acid sites in the material through Gaussian fitting. It can be seen that the main acidic site of the material is a medium strong acid.
The prepared sample is used as a catalyst for preparing biodiesel by transesterification of soybean oil and methanol, and the catalytic performance of the catalyst is examined. The reaction is carried out in a high-pressure reaction kettle, wherein the catalyst in the reaction kettle is 0.3g, the soybean oil is 10g, the methanol is 7.2g, the reaction temperature is 140 ℃, the stirring speed is 600r/min, and the reaction time is 1h, 2h, 3h, 4h and 5h respectively. After distilling off excess unreacted methanol, the product supernatant was analyzed on a gas chromatograph equipped with a hydrogen Flame Ionization Detector (FID). The catalytic evaluation result is shown in fig. 7, the conversion rate of soybean oil and the selectivity of biodiesel of the catalytic material in the reaction of catalyzing soybean oil and methanol are increased along with the increase of the reaction time, and the conversion rate of soybean oil is more than 99% and the selectivity of biodiesel is more than 97% when the reaction time reaches 5h, which indicates that the catalytic material has excellent catalytic activity of the transesterification reaction of soybean oil and methanol and the selectivity of biodiesel. In addition, as shown in fig. 8, the conversion rate of soybean oil and the selectivity of biodiesel of the catalytic material are not obviously changed in the process of being reused after regeneration, which indicates that the sample has very excellent reusability.
In combination with the products prepared in the above examples, the SO of the present invention4 2-/SnO2-ZrO2The solid acid catalytic material has a nano-stacking mesoporous structure, larger specific surface area and pore volume, and adjustable mesoporous diameter, wherein the mesoporous diameter is 2-30 nm, and the specific surface area is 110-190 m2Per gram, pore volume 0.16-0.3 cm3Adjustable in the range of/g. SO provided by the technical scheme4 2-/SnO2-ZrO2The solid acid catalytic material can be used as a catalyst for catalyzing the transesterification of soybean oil and methanol to prepare biodiesel; it can show very high soybean oil and methanol ester exchange activity and biodiesel selectivity. Under the conditions that the molar ratio of methanol to triolein is 20:1 at 140 ℃, the reaction lasts for 5 hours, the dosage of the catalyst is 3 percent of the mass of the soybean oil, the conversion rate of the soybean oil is not lower than 99 percent, and the content of the biodiesel in the product is not lower than 97 percent; in addition, SO prepared according to the invention4 2-/SnO2-ZrO2The solid acid catalytic material has excellent on-site performance, and the structure, texture and catalytic performance of the transesterification reaction of soybean oil and methanol are not changed after the solid acid catalytic material is repeatedly used for 7 times; the preparation method has simple and easy process and high reproduction rate.
Claims (3)
1. A solid acid material applied to catalytic synthesis of biodiesel is characterized in that: specifically, a zirconium source, a tin source, organic amine, organic ammonium salt, ammonia water, sulfuric acid, absolute ethyl alcohol and deionized water are used as raw materials, and the dosage of the raw materials meets the following requirements that the zirconium source is: organic ammonium salt: tin source: the molar ratio of the absolute ethyl alcohol = 900-1820: 125-270: 250-400: 25-140: 100000;
the raw material zirconium source is any one or a mixture of more of tetrahydrate zirconium sulfate, normal butanol zirconium, pentahydrate zirconium nitrate and octahydrate zirconium oxychloride;
the tin source is any one of tin tetrabromide, anhydrous tin chloride and pentahydrate tin chloride;
the organic amine is any one of triethanolamine or triisopropanolamine;
the organic ammonium salt is any one of hexadecyl trimethyl ammonium chloride, dioctyldimethyl ammonium bromide, didecyl dimethyl ammonium chloride or didecyl dimethyl ammonium bromide.
2. The solid acid material for catalyzing and synthesizing biodiesel according to claim 1, wherein: the solid acid catalytic material has a nano-stacking mesoporous structure, larger specific surface area and pore volume, and adjustable mesoporous diameter, wherein the mesoporous diameter is 2-30 nm, and the specific surface area is 110-190 m2Per gram, pore volume 0.16-0.3 cm3Adjustable in the range of/g.
3. A preparation method of a solid acid material applied to catalytic synthesis of biodiesel is characterized by specifically preparing the solid acid material according to the following method:
(1) according to the ratio of zirconium source to organic amine: organic ammonium salt: tin source: the molar ratio of the absolute ethyl alcohol = 900-1820: 125-270: 250-400: 25-140: 100000; completely dissolving a zirconium source, a tin source, organic amine and organic ammonium salt into absolute ethyl alcohol in sequence to obtain a clear solution;
(2) placing the clear solution in a hydrothermal kettle at the temperature of 60-90 ℃ for pre-crystallization treatment for 0.5-3 h to obtain a pre-crystallization product;
(3) dropwise adding ammonia water into the pre-crystallized product to adjust the pH = 9;
(4) the treated product is crystallized again in a hydrothermal kettle at the temperature of 100-140 ℃ for 24-48 h;
(5) washing the product after the secondary crystallization by using absolute ethyl alcohol until the product is neutral, and drying the washed product at the temperature of 60-80 ℃;
(6) drying the obtained product, roasting at 300-350 ℃, and removing the organic template;
(7) dipping each 1g of product without the organic template agent by using 10-20 ml of sulfuric acid solution with the concentration of 0.5-2 mol/L for 0.5-3 h;
(8) after the solution after impregnation is subjected to suction filtration, drying a filter cake at 100-120 ℃;
(9) and roasting the dried product at the temperature of 450-600 ℃ for 3-5 h to obtain the solid acid catalytic material.
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