CN111468149A - Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof - Google Patents
Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof Download PDFInfo
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- CN111468149A CN111468149A CN202010411407.9A CN202010411407A CN111468149A CN 111468149 A CN111468149 A CN 111468149A CN 202010411407 A CN202010411407 A CN 202010411407A CN 111468149 A CN111468149 A CN 111468149A
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- 229910018516 Al—O Inorganic materials 0.000 title claims abstract description 149
- 239000003225 biodiesel Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 184
- 238000000034 method Methods 0.000 claims abstract description 39
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 100
- 235000019198 oils Nutrition 0.000 claims description 45
- 241001048891 Jatropha curcas Species 0.000 claims description 39
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 229960001545 hydrotalcite Drugs 0.000 claims description 30
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 239000012684 catalyst carrier precursor Substances 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
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- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
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- 239000012153 distilled water Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 18
- 239000002585 base Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 239000011698 potassium fluoride Substances 0.000 description 79
- 239000000243 solution Substances 0.000 description 51
- 239000003921 oil Substances 0.000 description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000011148 porous material Substances 0.000 description 20
- 239000011575 calcium Substances 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001354 calcination Methods 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000008162 cooking oil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241000221089 Jatropha Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910018553 Ni—O Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 229910018507 Al—Ni Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
- 229960003988 indigo carmine Drugs 0.000 description 1
- 235000012738 indigotine Nutrition 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 235000003270 potassium fluoride Nutrition 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000003828 vacuum filtration Methods 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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Abstract
The invention discloses a novel biodiesel solid catalyst KF/Ca-Mg-Al-O and a preparation method and application thereof, wherein the preparation of the catalyst comprises the following steps: (1) preparing magnesium-aluminum composite metal oxide; (2) preparing a modified catalyst carrier; (3) and (3) preparing a catalyst. The KF/Ca-Mg-Al-O solid base catalyst is prepared by a coprecipitation method and an isovolumetric impregnation method, and compared with the traditional homogeneous catalyst, the catalyst prepared by the invention has the characteristics of high quality of easily separated products and the like in the using process; the catalyst prepared by the invention has the advantages of less alkali dissolution amount, good reutilization property, acid resistance, water resistance and saponification resistance in the using process. The catalyst has good catalytic activity, less alkali dissolution loss, simple preparation process, rich raw materials and low price, so the catalyst is a solid alkali catalyst suitable for popularization and application and can be effectively applied to the preparation of biodiesel.
Description
Technical Field
The invention relates to the technical field of preparation of solid catalysts and synthesis of biodiesel, in particular to a biodiesel catalyst, and specifically relates to a biodiesel catalyst KF/Ca-Mg-Al-O, and a preparation method and application thereof.
Background
At present, the worldwide available petrochemical resources are gradually reduced, along with the development of economy and society, the demand of human beings on petroleum energy is increased day by day, and the petrochemical resources gradually present the situation of short supply and short demand that biodiesel controls the emission of toxic pollutants and carcinogenic substances. The biodiesel is a renewable diesel fuel which can replace petroleum diesel and is prepared by taking oil crops or animal grease, food and beverage waste oil and the like as raw oil through ester exchange or other methods, has the advantages of renewability, cleanness and the like, and mainly comprises Fatty Acid Methyl Ester (FAME). The synthesis of low cost biodiesel is not only a major challenge for manufacturers, but also a huge challenge for scientists and researchers.
At present, the mass production of biodiesel is mainly realized by synthesizing biodiesel through ester exchange. Although the reaction efficiency is high, the separation of the product after the reaction is difficult, and a large amount of pollutants are discharged. The solid base catalyst is adopted to replace a homogeneous catalyst, so that the product and the catalyst are easy to separate, the discharge of a large amount of waste liquid can be avoided, the environmental pollution is effectively prevented, and meanwhile, the solid catalyst has the characteristics of easy activation and regeneration and convenient continuous operation.
According to the existing report, the chemical reagent grade used in the preparation process of most catalysts of the biodiesel is Chemical Pure (CP) or experimental reagent (L R), the preparation process has high requirements on the reagent conditions, the consumption cost is high, the experimental conditions are harsh, the performance of some catalysts on the reutilization property is poor, and the cost of regenerated catalysts is high.
The method for industrially preparing biodiesel by using caustic alkali such as sodium hydroxide or potassium hydroxide or a solid acid catalyst has the characteristic of high yield of biodiesel, but has the defects of corrosion and scaling of equipment, blockage of pipelines, difficulty in separation and aftertreatment of the catalyst and the like, and can cause environmental pollution to a certain extent. Therefore, supported solid base catalysts have been further developed. In patent CN106345448A, it is reported that a plurality of single components such as shell powder, activated carbon, ZnO, etc. are used as carriers to load active components to prepare biodiesel. Patent CN105642268A reports that a solid base catalyst is prepared by using nitrates of cerium, lanthanum or lithium, calcium, magnesium, and aluminum as raw materials, urea as a precipitant, and preparing hydrotalcite-like compound by a uniform precipitation method, and then calcining at high temperature, whereas the catalyst in the prior art is not only complex to prepare and the yield of the product is not very high.
The Ca-Al-O, Mg-Al-O and Zn-Al-O composite oxides are independently used as biodiesel catalysts and have been reported in some researches, and the catalytic activity sequence of the composite oxides is as follows; Ca-Al-O > Mg-Al-O > Zn-Al-O; the acid-resistant and water-resistant abilities are in the sequence of Zn-Al-O, Mg-Al-O, Ca-Al-O, and the Ca-Al-O catalyst has strong activity and high catalytic reaction rate, but has poor acid-resistant and water-resistant abilities. The requirements on the raw materials are severe: the Zn-Al-O catalyst has strong acid and water resistance, loose requirements on raw materials, poor activity and slow catalytic reaction rate.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a novel biodiesel solid catalyst KF/Ca-Mg-Al-O and a preparation method thereof, the catalyst prepared by the invention has the advantages of good activity, water resistance, acid resistance and saponification resistance, and simultaneously has the characteristics of easy product separation, high quality and the like, and solves the problems existing in the process of preparing biodiesel by taking the existing metal oxide as a carrier, for example, a reaction mixture is easy to form slurry which is difficult to separate, the product cannot be effectively separated, and finally, the biodiesel which can be utilized is few and has poor quality. Meanwhile, experimental reagents used in the preparation process of the catalyst are all in industrial grade, the production cost is low, and the requirements on experimental conditions are not strict.
The invention relates to a preparation method and application of a novel biodiesel solid catalyst KF/Ca-Mg-Al-O.
The technical scheme is as follows: in order to achieve the above purpose, the invention provides a preparation method of a novel biodiesel solid catalyst KF/Ca-Mg-Al-O, which comprises the following steps:
(1) mixing Mg (Cl)2·6H2O and Al (Cl)3·6H2Preparing the solution A from the O, stirring, adding an ammonia water solution until the pH value of the solution A is 10-11, stopping adding the ammonia water solution, standing, crystallizing, filtering, and drying filter residues to obtain the magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite to obtain Mg-Al-O;
(2) adding Mg-Al-O to Ca (OH)2Dipping in the solution, drying to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O at high temperature to obtain a biodiesel catalyst carrier Ca-Mg-Al-O;
(3) adding a catalyst carrier Ca-Mg-Al-O into a KF solution, impregnating, drying to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O at high temperature to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Wherein, the Mg (Cl) in the step (1)2·6H2O and Al (Cl)3·6H2O is used in the amount of Mg2+And Al3+Calculated by the molar ratio of n (Mg)2+):n(Al3+)＝1-5:1. The stirring speed in the step (1) is 500-. Crystallizing at 80-100 ℃ for 2-4h, pouring the crystallized mixture into a Buchner funnel connected with a filter flask for suction filtration, washing filter residue to be neutral, and drying at 80-100 ℃ for 4-6h to obtain the magnesium-aluminum hydrotalcite; the magnesium-aluminum hydrotalcite is roasted for 2 to 5 hours at the temperature of 600 ℃ and 900 ℃. Adding ammonia water until the pH value is 10-11 in the step (1).
Step (2) said Ca (OH)2The concentration of the solution is 1-5 wt%, Mg-Al-O and Ca (OH)2The solution ratio is 1:1.05g/m L, the impregnation in the step (2) is carried out for 4-6h at 20-25 ℃, and is dried for 4-6h at 80-100 ℃ to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and the modified catalyst carrier precursor Ca-Mg-Al-O is roasted for 3-4h at 600-900 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O.
The concentration of the KF solution in the step (3) is 10-30 wt%, the ratio of the Ca-Mg-Al-O solution to the KF solution is 1:1.1g/m L, the impregnation in the step (3) is carried out for 12-16h at 20-25 ℃, the catalyst precursor KF/Ca-Mg-Al-O is obtained after drying for 4-6h at 80-100 ℃, and the catalyst precursor KF/Ca-Mg-Al-O is roasted for 2-7h at the temperature of 900 ℃ of 400-.
Preferably, the stirring speed in the step (1) is 600 r/min; crystallizing at 90 ℃ for 3h, performing vacuum filtration, washing filter residues to be neutral, and drying at 80 ℃ for 6h to obtain magnesium-aluminum hydrotalcite; the magnesium-aluminum hydrotalcite is roasted for 3 hours at the temperature of 700 ℃. Ammonia water was added to a pH of 10.
Preferably, the impregnation in the step (2) is carried out at 25 ℃ for 6h, and the impregnation is carried out at 80 ℃ for 6h to obtain a modified catalyst carrier precursor Ca-Mg-Al-O; the modified catalyst support precursor Ca-Mg-Al-O was calcined at 700 ℃ for 3 h.
Preferably, the impregnation in the step (3) is carried out at 25 ℃ for 12h, and the catalyst precursor KF/Ca-Mg-Al-O is obtained after drying at 80 ℃ for 6 h.
The biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by the preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O is provided.
The biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by the preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O is applied to the catalytic preparation of biodiesel.
The application comprises the following specific processes:
the method comprises the steps of putting a certain amount of barbadosnut oil into a separating funnel, adding methanol to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, plugging a stopper, shaking, standing, pouring out the upper layer of methanol after layering, adding methanol into the lower layer of barbadosnut oil again to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, repeating the operation until the acid value of the barbadosnut oil is determined to be less than 1mg KOH/g, and taking the treated barbadosnut oil as a raw material for preparing the biodiesel.
Carrying out reaction in a single-neck flask under the conditions that methanol is pretreated barbadosnut seed oil (mol: mol) is 14:1, and the mass of a catalyst KF/Ca-Mg-Al-O is as follows: the mass of the pretreated barbadosnut seed oil is 0.04%, the reaction temperature is 65 ℃, and the reaction time is controlled to be 3 h.
After the reaction is finished, the reactant is subjected to rotary evaporation to remove the unreacted methanol in the product, the pressure is 0.03MPa, the temperature is 55 ℃, and the stirring speed is controlled at 30 r/min.
And placing the reactant in a separating funnel, standing the catalyst and glycerol to be settled at the bottom of the separating funnel, discharging the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times until the crude biodiesel layer is neutral, and removing a small amount of methanol residues, alkaline substances dropped off by the solid base catalyst in the reaction process and the like. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil. The KF/Ca-Mg-Al-O supported solid base catalyst prepared by the invention is different from a supported catalyst taking a single component as a carrier, and a composite catalyst carrier is prepared by taking magnesium and aluminum chloride as raw materials. Meanwhile, the potassium fluoride is loaded, and higher biodiesel yield is obtained compared with a method of directly taking the composite metal oxide as a biodiesel catalyst. The catalyst has certain acid resistance, water resistance and soap resistance while using Mg-Al-O as a catalyst carrier. This is achieved byIn addition, after the preparation of the Mg-Al-O carrier is finished, Ca (OH) is used2The catalyst carrier is modified, so that the acid resistance, water resistance and soap resistance of the catalyst carrier are further improved, and the catalyst carrier has a porous structure, the specific surface area is increased, and active sites are increased when the catalyst carrier is combined with KF through being calcined as can be observed from an SEM picture.
The preparation method comprises the steps of firstly preparing the magnesium-aluminum composite metal oxide; preparing a modified catalyst carrier; preparing a catalyst; the KF/Ca-Mg-Al-O solid base catalyst is prepared by a coprecipitation method and an isovolumetric impregnation method. Compared with the traditional homogeneous catalyst, the catalyst prepared by the invention has the characteristics of high quality of easily separated products and the like in the using process; compared with the traditional heterogeneous solid alkali catalyst, the catalyst prepared by the invention has the advantages of less alkali dissolution amount, good reusability, acid resistance, water resistance and saponification resistance in the using process.
The catalyst is designed by utilizing Mg2+And Al3+Coprecipitating in alkaline environment to obtain Mg-Al hydrotalcite, calcining at high temperature to obtain Mg-O-Al hydrotalcite with porous Mg-O-Al structure, and using free Ca2+Part of Mg in the structure2+Displacing to form Ca-O-Al, loading KF to form Ca-O-K, calcining at high temperature to form KCaF3And is loaded on the surface of the catalyst.
Has the advantages that: compared with the prior art, the invention has the following advantages:
according to the biodiesel catalyst KF/Ca-Mg-Al-O prepared by the invention, magnesium-aluminum hydrotalcite is prepared by a coprecipitation method through a mixed solution of magnesium chloride and aluminum chloride, the surface of the magnesium-aluminum hydrotalcite is modified by calcium hydroxide to generate more acid-base active centers, a catalyst carrier Ca-Mg-Al-O is prepared by calcination, KF is loaded on the surface of the carrier through an isometric impregnation method, the catalyst KF/Ca-Mg-Al-O is prepared by calcination, TG characterization is carried out on the catalyst and a precursor thereof, and alkali strength, XRD and SEM characterization is carried out on the catalyst. The characterization result shows that the catalyst forms new KCaF after being loaded with KF and subjected to high-temperature calcination3The substance is a component having a strong catalytic activity.
The Jatropha curcas seed oil used in the invention is a non-edible oil with high acid value, which is widely available, cheap and easy to obtain, and can cause harm to human body when being eaten by mistake, and the biodiesel prepared by using the Jatropha curcas seed oil as a raw material has low cost, does not contain sulfur, is pollution-free and is environment-friendly. The catalyst prepared by the invention takes the barbadosnut seed oil as a raw material, and the reusability of the catalyst is researched, so that the catalyst still has higher catalytic activity after being reused for 7 times. By transesterifying 4 jatropha seed oils of different acid numbers, the results were shown to be insensitive to acid number variations. Therefore, the catalyst has better catalytic activity and less alkali dissolution loss, and the catalyst has simple preparation process, rich raw materials and low price, so the catalyst is a solid alkali catalyst suitable for popularization and application and can be effectively applied to the preparation of biodiesel.
The innovation point of the invention is that Ca is used2+The catalyst carrier is modified, and Ca is different from the prior catalyst taking Mg-Al-O as the carrier2+Enables the catalyst to form KCaF3The catalytic capability is enhanced; the preparation method is simple, and preparation can be realized in most experimental environments; the catalyst can be repeatedly used for many times, can still keep higher catalytic activity, saves cost and is green and environment-friendly; the biodiesel and the catalyst are in different two phases, and the product is easy to separate; the catalyst has low use ratio and relatively large particles, is easy to settle after reaction, cannot be mixed with reactants to form slurry, but also has good catalytic effect due to a plurality of pore passages and large specific surface area.
Drawings
FIG. 1 is an XRD spectrum of a solid base catalyst of Mg-Al-O, CaO, KF and KF/Ca-Mg-Al-O;
FIG. 2 is an SEM micrograph of Ca-Mg-Al-O and KF/Ca-Mg-Al-O;
FIG. 3 is a schematic diagram of the repetitive use study of the KF/Ca-Mg-Al-O catalyst.
Detailed description of the invention
The invention is further illustrated by the following figures and examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures, in which specific conditions are not indicated in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturer. The specific surface area, pore channel, pore diameter and pore volume in the present invention are defined as follows.
Specific surface area: the sum of the internal and external surface areas of the catalyst per unit mass is called the specific surface area of the catalyst.
Pore canal: the catalyst pellet has microporous channel.
Pore diameter: refers to the shape and size of the channels in the porous solid. The pores are rather highly irregular, usually viewed as circles and the size of the pores is expressed in terms of their radius.
Pore volume: the sum of all pore volumes within the catalyst.
Example 1
(1) Mixing Mg2+And Al3+The molar ratio is as follows: n (Mg)2+):n(Al3+) 1:1, 2.0330g of Mg (Cl)2·6H2O and 2.4143g of Al (Cl)3·6H2Dissolving O in 300m L deionized water to prepare a solution A, slowly stirring and adding 28% (v/v, ml/ml) ammonia water solution into the solution A, stirring at the speed of 600r/min until the pH value of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter bottle for suction filtration, washing filter residues with water to pH 7, drying at 80 ℃ for 6 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at the temperature of 700 ℃ for 4 hours to obtain Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1m L of 1 wt% Ca (OH)2Dipping the solution for 6h at the temperature of 25 ℃, and drying the solution for 6h at the temperature of 80 ℃ to obtain the modified catalyst carrier precursor Ca-Mg-Al-O. Roasting the precursor Ca-Mg-Al-O of the modified catalyst carrier for 3 hours at 600 ℃ to obtain the carrier Ca-Mg-Al-O of the biodiesel catalyst.
(3) Adding 2g of catalyst carrier Ca-Mg-Al-O into 10 wt% of KF solution of 2.2m L, dipping for 12h at 25 ℃, drying for 4h at 100 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O, roasting the catalyst precursor KF/Ca-Mg-Al-O at 400 ℃ for 7h to obtain the biodiesel catalyst KF/Ca-Mg-Al-O, and obtaining the catalyst S1。
The specific method for synthesizing the biodiesel by the catalysis of the KF/Ca-Mg-Al-O solid base catalyst comprises the following steps:
the method comprises the steps of putting a certain amount of barbadosnut oil into a separating funnel, adding methanol to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, plugging a stopper, shaking, standing, pouring out the upper layer of methanol after layering, adding methanol into the lower layer of barbadosnut oil again to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, repeating the operation until the acid value of the barbadosnut oil is determined to be less than 1mg KOH/g, and taking the treated barbadosnut oil as a raw material for preparing the biodiesel.
The reaction was carried out in a single-neck flask, i.e. methanol: the pretreated barbadosnut seed oil (mol: mol) ═ 14:1, the reaction temperature is controlled at 65 ℃, and the catalyst: the mass ratio of the pretreated barbadosnut seed oil is 0.04%, and the reaction time is controlled to be 3 h.
After the reaction is finished, the reactant is poured into a pear-shaped bottle for rotary evaporation, and the unreacted methanol in the product is removed, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30 r/min.
And placing the reactant in a separating funnel, standing, discharging the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil.
Example 2
(1) Mixing Mg2+And Al3+The molar ratio is as follows: n (Mg)2+):n(Al3+) (iii) 3:1, 6.0990g of Mg (Cl)2·6H2O and 2.4143g of Al (Cl)3·6H2Dissolving O in 300m L deionized water to obtain solution A, adding 28% (v/v, ml/ml) ammonia water solution into solution A while stirring at 600r/min until pH of solution A is 10.5, stopping adding ammonia water solution, standing, crystallizing at 100 deg.C for 2 hr, filtering the crystallized mixture in Buchner funnel connected with filter flask, washing the filter residue with water to pH 7, drying at 90 deg.C for 5 hr to obtain Mg-Al hydrotalcite, and adding Mg-Al hydrotalcite at 600 deg.CAnd (4) roasting the hydrotalcite for 5 hours to obtain Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1m L of 3 wt% Ca (OH)2Soaking the catalyst in the solution at 22 ℃ for 5h, and drying the solution at 90 ℃ for 5h to obtain a modified catalyst carrier precursor Ca-Mg-Al-O. Roasting the precursor Ca-Mg-Al-O of the modified catalyst carrier for 3.5 hours at 700 ℃ to obtain the carrier Ca-Mg-Al-O of the biodiesel catalyst.
(3) Adding 2g of catalyst carrier Ca-Mg-Al-O into 20 wt% KF solution of 2.2m L, dipping for 14h at 22 ℃, drying for 5h at 90 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O, roasting the catalyst precursor KF/Ca-Mg-Al-O for 5h at 600 ℃ to obtain biodiesel catalyst KF/Ca-Mg-Al-O, and obtaining catalyst S2。
The specific method for synthesizing the biodiesel by the catalysis of the KF/Ca-Mg-Al-O solid base catalyst comprises the following steps:
the method comprises the steps of putting a certain amount of barbadosnut oil into a separating funnel, adding methanol to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, plugging a stopper, shaking, standing, pouring out the upper layer of methanol after layering, adding methanol into the lower layer of barbadosnut oil again to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, repeating the operation until the acid value of the barbadosnut oil is determined to be less than 1mg KOH/g, and taking the treated barbadosnut oil as a raw material for preparing the biodiesel.
The reaction was carried out in a single-neck flask, i.e. methanol: pretreated jatropha seed oil (mol: mol) ═ 14:1, the reaction temperature was controlled at 65 ℃, catalyst: the mass ratio of the pretreated barbadosnut seed oil is 0.04%, and the reaction time is controlled to be 3 h.
After the reaction is finished, the reactant is poured into a pear-shaped bottle for rotary evaporation, and the unreacted methanol in the product is removed, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30 r/min.
And placing the reactant in a separating funnel, standing, discharging the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil.
The XRD patterns of the KF, CaO, Mg-Al-O and KF/Ca-Mg-Al-O catalysts produced in this example are shown in FIG. 1. As can be observed in XRD patterns of the solid base catalysts of Mg-Al-O, CaO, KF and KF/Ca-Mg-Al-O, the corresponding peaks of Mg-Al-O at 65 ℃ disappear, the broad peaks at about 37 ℃ disappear, and new diffraction peaks at about 55 ℃ disappear after modification with Ca, it can be confirmed that CaO is not simply dispersed on the surface of the KF/Ca-Mg-Al-O catalyst, but forms a new composite metal oxide Ca-Mg-Al-O with Mg-Al-O by high-temperature calcination as a catalyst carrier. The disappearance of the characteristic diffraction peak of KF carried by impregnation proves that KF is not simply carried on the surface of the body and a new diffraction peak is generated at 13 deg., so that KF forms a substance KCaF having catalytic activity with the catalyst carrier after high-temperature calcination3。
SEM spectra of Ca-Mg-Al-O and KF/Ca-Mg-Al-O produced in this example are shown in FIG. 2. FIGS. 2(a) and 2(b) are SEM spectra of Ca-Mg-Al-O and catalyst KF/Ca-Mg-Al-O calcined at 700 ℃. The surface of the catalyst KF/Ca-Mg-Al-O loaded with KF has a larger particle structure, and the flaky structure on the particle surface is probably caused by the fact that the KF is loaded, which can explain the phenomenon that the specific surface area of the catalyst is slightly reduced after the catalyst is loaded. And the solid surface has a porous structure, which shows that the catalyst has a pore channel in the preparation process, so that the catalyst can be better combined with a reactant, and a better catalytic effect is provided. It is further explained that the interaction exists between the loaded KF and the carrier, the KF and CaO form a new substance KCaF after calcination instead of being simply loaded on the surface3And the XRD analysis result is verified. Furthermore, the method is simple. In the invention, the difference between fig. 2(a) and fig. 2(b) shows that the channel structure appears in b, but does not appear in a, and table 1 is combined to show that the catalyst has good catalytic effect due to the fact that the catalyst has many channels and large specific surface area. Because of the necessary conditions for the collision-type reaction between the reactant molecules to proceed in the chemical reaction. Due to the increase of the specific surface area, the occurrence of the pore channels improves the contact and collision probability of the reaction raw materials and the surface of the catalyst, and can improve the catalysis of the reactionEfficiency.
Example 3
(1) Mixing Mg2+And Al3+The molar ratio is as follows: n (Mg)2+):n(Al3+) (iii) 5:1, 10.1650g of Mg (Cl)2·6H2O and 2.4143g of Al (Cl)3·6H2Dissolving O in 300m L deionized water to prepare a solution A, slowly stirring and adding 28% (v/v, ml/ml) ammonia water solution into the solution A, stirring at the speed of 600r/min until the pH value of the solution A is 11, stopping adding the ammonia water solution, standing, crystallizing at 80 ℃ for 4 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter bottle for suction filtration, washing filter residues with water to pH 7, drying at 100 ℃ for 4 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at 900 ℃ for 2 hours to obtain Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1m L of 5 wt% Ca (OH)2Dipping the solution for 4h at the temperature of 20 ℃, and drying the solution for 4h at the temperature of 100 ℃ to obtain the precursor Ca-Mg-Al-O of the modified catalyst carrier. Roasting the modified catalyst carrier precursor Ca-Mg-Al-O for 4 hours at 900 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O.
(3) Adding 2g of catalyst carrier Ca-Mg-Al-O into 30 wt% KF solution of 2.2m L, dipping for 16h at 20 ℃, drying for 6h at 80 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O, roasting the catalyst precursor KF/Ca-Mg-Al-O for 2h at 900 ℃ to obtain biodiesel catalyst KF/Ca-Mg-Al-O, and obtaining catalyst S3。
The specific method for synthesizing the biodiesel by the catalysis of the KF/Ca-Mg-Al-O solid base catalyst comprises the following steps:
the method comprises the steps of putting a certain amount of barbadosnut oil into a separating funnel, adding methanol to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, plugging a stopper, shaking, standing, pouring out the upper layer of methanol after layering, adding methanol into the lower layer of barbadosnut oil again to enable the mass-to-volume ratio of the barbadosnut oil to the methanol (g: m L) to be 1:2.5, repeating the operation until the acid value of the barbadosnut oil is determined to be less than 1mg KOH/g, and taking the treated barbadosnut oil as a raw material for preparing the biodiesel.
The reaction is carried out in a single-neck flask, namely methanol and the pretreated barbadosnut oil (mol: mol) are 14:1, the reaction temperature is controlled at 65 ℃, the catalyst and the pretreated barbadosnut oil (mass ratio) are 0.04%, and the reaction time is controlled at 3 h.
After the reaction is finished, the reactant is poured into a pear-shaped bottle for rotary evaporation, and the unreacted methanol in the product is removed, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30 r/min.
And placing the reactant in a separating funnel, standing, discharging the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil.
Comparative example 1
(1) Mixing Mg2+And Al3+The molar ratio is as follows: n (Mg)2+):n(Al3+) (iii) 3:1, 6.0990g of Mg (Cl)2·6H2O and 2.4143g of Al (Cl)3·.6H2Dissolving O in 300m L deionized water to prepare a solution A, slowly stirring and adding 28% (v/v, ml/ml) ammonia water solution into the solution A, stirring at the speed of 600r/min until the pH value of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter bottle for suction filtration, washing filter residues with water to pH 7, drying at 80 ℃ for 6 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at the temperature of 700 ℃ for 4 hours to obtain Mg-Al-O.
(2) 2g of catalyst carrier Mg-Al-O was added to a 20 wt% KF solution of 2.2m L, immersed at 25 ℃ for 12 hours, dried at 80 ℃ for 6 hours to obtain a catalyst precursor D1. Roasting the catalyst precursor at 600 ℃ for 5h to obtain the biodiesel catalyst, namely the catalyst D1。
Catalyst D1The specific method for catalytically synthesizing biodiesel was the same as in example 2.
Comparative example 2
(1) Mixing Mg2+And Al3+The molar ratio is as follows: n (Mg)2+):n(Al3+) (iii) 3:1, 6.0990g of Mg (Cl)2·6H2O and 2.4143g of Al (Cl)3·6H2Dissolving O in 300m L deionized water to prepare a solution A, slowly stirring and adding 28% (v/v, ml/ml) ammonia water solution into the solution A, stirring at the speed of 600r/min until the pH value of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter bottle for suction filtration, washing filter residues with water to pH 7, drying at 80 ℃ for 6 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at the temperature of 700 ℃ for 4 hours to obtain Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1m L of 3 wt% Ca (OH)2Soaking in the solution at 25 deg.C for 6 hr, and drying at 80 deg.C for 6 hr. Roasting at 700 deg.C for 3h to obtain biodiesel catalyst called catalyst D2。
Catalyst D2The specific method for catalytically synthesizing biodiesel was the same as in example 2.
Comparative example 3 is the same as the method of inventive example 2 except that 2g of Mg-Al-O was added to 2.1m L of 7 wt% Ca (OH) in step (2)2And (3) solution.
Comparative example 4 is the same as the process of inventive example 2 except that in step (3) 2g of catalyst support Ca-Mg-Al-O was taken and added to a 40 wt% solution of KF at 2.2m L.
Comparative example 5 is a CaO-ZnO catalyst prepared by a coprecipitation method in a major paper published by deutsche university of hebei, 2017, research on calcium-based solid base catalysts for preparing biodiesel.
Comparative example 6 preparation of CaO/ZrO by template method, published in petrochemical 2015 43, No. 7, 774 and No. 778 Liuliuchen2CaO/ZrO prepared in process of catalyzing rapeseed oil to synthesize biodiesel by catalyst2A catalyst.
The catalyst used in comparative example 7 was the catalyst used in example 2, except that the raw material used in the process for producing biodiesel was waste cooking oil (and the same pretreatment process as in example 2 was used).
The BET analysis of the catalysts prepared in the above examples 1 to 3 and comparative examples 1 to 6 and the GC analysis of the biodiesel prepared therefrom were carried out to calculate the biodiesel yield, and the results are shown in Table 1.
TABLE 1 physical Properties of the catalyst and its biodiesel production yield
As can be seen from Table 1, the specific surface area, pore diameter and pore volume of comparative examples 1-2 are slightly larger than those of examples 1-3, because the pores are formed during the process of calcining Mg-Al-O from Mg-Al hydrotalcite at high temperature, and the pores are reduced to some extent after Ca modification and KF loading. However, the biodiesel yields of examples 1-3 were higher than D1This is due to Ca2+The presence of (A) displaces a portion of Mg in the Mg-Al-O lattice2+And Al3+So that the alkalinity of the biodiesel is enhanced, and the biodiesel has higher yield. And D2It is because it does not carry the catalytically active ingredient KF and does not have a good catalytic performance.
S from Table 12And D1And D3It can be seen that Ca was increased under otherwise identical conditions2+The amount of Ca does not increase the biodiesel yield all the time2+The presence of (b) can make the alkalinity thereof enhanced, but the increase is too much, the surface will be covered by excessive CaO after calcination, resulting in a decrease in specific surface area, an increase in pore size and pore volume, and a decrease in biodiesel yield.
S from Table 12And D2And D4It can be seen that KF is essential for effective catalytic activity enhancement, but too much addition does not result in a constant increase in biodiesel yield because KF already occupies all the surface active sites and forms the catalytically active species KCaF after high temperature calcination3Further increase in KF does not bind to the active sites, the binding sites are saturated, and because of the inability to bind, increasing KF results in a certain amount of catalyst with a proportionally lower amount of catalytically active material.
S from Table 12And D5And D6It can be seen that the surface structure of the catalyst of the present invention is advantageous in terms of the catalyst ratioWhen the difference between the area, the pore diameter and the pore volume is larger, the larger specific surface area can be more beneficial to catalytic reaction.
In addition, the catalyst of example 2 was subjected to the alkali strength test by taking fresh 5.0g of the catalyst, adding 25.0m L cyclohexane, shaking for 30min, then adding 2-3 drops of benzene solution containing 0.1% phenolphthalein indicator, observing the color change on the surface of the catalyst after equilibrium adsorptionaValue 9.8), indigo carmine (pK)aValue 12.2), 2, 4-dinitroaniline (pK)aValue 15.0), 4-nitroaniline (pK)aValue 18.4). The surface color of the catalyst is not obviously changed after the catalyst is used for seven times, which indicates that the alkali strength of the catalyst is not greatly changed.
The results of the reusability test of the catalyst in example 2 are shown in fig. 3, which comprises the steps of centrifuging the mixture of the catalyst and glycerol discharged from the lower layer of the separating funnel after standing, separating the catalyst, heating and refluxing the used catalyst with 50m L methanol at 50 ℃ for 1 hour, filtering, and drying in vacuum at 120 ℃ for 2 hours to obtain a regenerated catalyst, continuing to catalyze the transesterification reaction (similar to the preparation of biodiesel in example 2), repeating the regeneration according to the above steps after the reaction is finished, wherein the biodiesel yield is generally decreased after 7 times, the yield of biodiesel prepared by using the catalyst for the first time is 98.51% in fig. 3, but is still 88.23% after 7 times of use, and is decreased by only 10.28% after 7 times of repetition.
TABLE 2 Difference in recyclability between different catalysts
As can be seen from Table 2, the KF/Ca-Mg-Al-O catalyst was the catalyst prepared in example 2 of the present invention, Ba (OH)2The catalyst is' Ba (OH) published in Panlishuang 2017 of Jiangnan university2The catalyst in the Master thesis is used for catalyzing the methyl esterification of the castor oil to prepare the biodiesel. K2CO3the/Al-Ni-O catalyst is solid base K which is published by Wuxianni et Al in Industrial catalysis 2016, 24, vol.4, page 61-632CO3Al-Ni and K2CO3Catalyst prepared in the process of preparing biodiesel by Al-Ni-O catalysis. The KF/MMT catalyst is a catalyst prepared by Van-Fenglan et al in the article "preparation of KF/MMT solid base catalyst and catalytic transesterification" published in oil and fat chemical engineering, volume 38, page 56-59 of 2013. NaOH and H2SO4Is a catalyst prepared by Chengyu et al in the 'research on the process for preparing biodiesel by homogeneously catalyzing waste cooking oil' in the article published by Chengyu et al in the petroleum technology and application, 2008, volume 26, stage 5, 415 and 420. Compared with the biodiesel yield of the catalyst after repeated use and repeated use, the catalyst of the invention is superior. The homogeneous catalyst is difficult to realize in the aspect of recycling, the recycling causes high cost, and used acid or alkali can remain in the product biodiesel, so that the quality of the product biodiesel is not high.
In comparative example 7 of Table 2, the catalyst of example 2 of the present invention was excellent in the recyclability of waste oils and fats, though the raw materials were different. The raw material of the barbadosnut seed oil is easy to obtain and low in cost, and is more suitable for being used as a raw material for producing the biodiesel, and the waste cooking oil is usually in a dispersed state when being purchased at a designated site of each waste oil, the amount of a single purchasing site is small, the collection is troublesome, a large amount of manpower and material resources are consumed, so that the comprehensive cost of the raw material is relatively high, and therefore, the catalyst for catalyzing the barbadosnut seed oil can achieve the purpose of preparing the low-cost biodiesel, and is superior to a homogeneous catalyst in recycling property.
Compared with the prior art, the catalyst has more times of repetition, and the yield of the biodiesel is not obviously reduced after the catalyst is repeatedly used. Therefore, the catalyst prepared by the invention is superior to the catalyst in recycling property, and the application of the catalyst in industrial production can save production cost.
The catalyst of example 2 was tested for acid resistance and recyclability, comprising the steps of: the four kinds of soybeans having acid values of 0.24mg KOH/g, 0.39mg KOH/g, 0.65mg KOH/g, and 1.04mg KOH/g were subjected to transesterification, respectively. The reaction process is as follows: the reaction is carried out in a single-neck flask, namely methanol and the pretreated barbadosnut oil (mol: mol) are 14:1, the reaction temperature is controlled at 65 ℃, the catalyst and the pretreated barbadosnut oil (mass ratio) are 0.04%, and the reaction time is controlled at 3 h. After the reaction is finished, the reactant is poured into a pear-shaped bottle for rotary evaporation, and the unreacted methanol in the product is removed, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30 r/min. And placing the reactant in a separating funnel, standing, discharging the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil. The biodiesel yield of the reaction products is measured to be 97.22 percent, 96.18 percent, 95.36 percent and 94.55 percent respectively, and is reduced by 2.67 percent, which proves that the catalyst has good acid resistance.
Example 4
Example 4 was prepared identically to example 2, except that: crystallizing at the temperature of 80 ℃ for 4 hours, pouring the crystallized mixture into a Buchner funnel connected with a filter flask for suction filtration, washing filter residues to be neutral, drying at the temperature of 80 ℃ for 6 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at the temperature of 600 ℃ for 5 hours; and (2) adding ammonia water until the pH value of the solution A is 11. And (2) dipping for 6h at 20 ℃, drying for 6h at 80 ℃ to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O for 4h at 600 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O. And (3) soaking at 20 ℃ for 16h, and drying at 80 ℃ for 6h to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O at 400 ℃ for 7h to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Example 5
Example 5 was prepared identically to example 2, except that: and (2) crystallizing at 100 ℃ for 2h, pouring the crystallized mixture into a Buchner funnel connected with a filter flask for suction filtration, washing filter residues to be neutral, drying at 100 ℃ for 4h to obtain the magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at 900 ℃ for 2 h. And (3) dipping for 4h at 25 ℃, drying for 4h at 100 ℃ to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O for 3h at 900 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O. And (3) dipping for 12h at 25 ℃, drying for 4h at 100 ℃ to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O for 2h at 900 ℃ to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Claims (10)
1. A preparation method of a novel biodiesel solid catalyst KF/Ca-Mg-Al-O is characterized by comprising the following steps:
(1) mixing Mg (Cl)2·6H2O and Al (Cl)3·6H2Preparing the solution A from the O, stirring, adding an ammonia water solution into the solution A, standing, crystallizing, filtering, and drying filter residues to obtain the magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite to obtain Mg-Al-O;
(2) adding Mg-Al-O to Ca (OH)2Dipping in the solution, drying to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O at high temperature to obtain a biodiesel catalyst carrier Ca-Mg-Al-O;
(3) adding a catalyst carrier Ca-Mg-Al-O into a KF solution, impregnating, drying to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O at high temperature to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
2. The method for preparing the novel solid catalyst KF/Ca-Mg-Al-O for biodiesel according to claim 1, wherein said Mg (Cl) in step (1)2·6H2O and Al (Cl)3·6H2O is used in the amount of Mg2+And Al3+Calculated by the molar ratio of n (Mg)2+):n(Al3+)＝1-5:1。
3. The preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O as claimed in claim 1, wherein the crystallization in step (1) is preferably performed at 80-100 ℃ for 2-4h, the crystallized mixture is poured into a Buchner funnel connected with a filter flask for suction filtration, the filter residue is washed to be neutral, and dried at 80-100 ℃ for 4-6h to obtain the magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at the temperature of 600-900 ℃ for 2-5 h; and (2) adding ammonia water into the solution A to ensure that the pH value of the solution A is 10-11.
4. The method for preparing the novel solid catalyst KF/Ca-Mg-Al-O for biodiesel according to claim 1, wherein the Ca (OH) in the step (2)2The concentration of the solution is 1-5 wt%, Mg-Al-O and Ca (OH)2The solution ratio was 1:1.05g/m L.
5. The preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O as claimed in claim 1, wherein the impregnation in step (2) is carried out at 20-25 ℃ for 4-6h, and dried at 80-100 ℃ for 4-6h to obtain the modified catalyst carrier precursor Ca-Mg-Al-O, and the modified catalyst carrier precursor Ca-Mg-Al-O is calcined at 600-900 ℃ for 3-4h to obtain the biodiesel catalyst carrier Ca-Mg-Al-O.
6. The preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O as claimed in claim 1, wherein the concentration of the KF solution in step (3) is 10-30 wt%, and the ratio of the Ca-Mg-Al-O catalyst carrier to the KF solution is 1:1.1g/m L.
7. The preparation method of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O as claimed in claim 1, wherein the impregnation in step (3) is carried out at 20-25 ℃, 12-16h, and 4-6h at 80-100 ℃ for drying to obtain the catalyst precursor KF/Ca-Mg-Al-O, and the catalyst precursor KF/Ca-Mg-Al-O is calcined at 400-900 ℃ for 2-7h to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
8. The novel biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by the method for preparing the biodiesel solid catalyst KF/Ca-Mg-Al-O according to claim 1.
9. The application of the novel biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by the preparation method of the biodiesel solid catalyst KF/Ca-Mg-Al-O in preparing biodiesel by catalysis in claim 1.
10. The application according to claim 9, wherein the specific process of the application is as follows:
the reaction conditions were controlled as methanol: the mass of the catalyst KF/Ca-Mg-Al-O is as follows: the mass of the pretreated barbadosnut seed oil is 0.04 percent, the reaction temperature is controlled at 65 ℃, and the reaction time is controlled at 3 hours; after the reaction is finished, carrying out rotary evaporation on reactants to remove the unreacted methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is 30 r/min; pouring the reactant into a separating funnel, standing, removing the lower layer of glycerol and the catalyst, taking the upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate into the upper layer of biodiesel oil layer, dehydrating, shaking, centrifuging, and collecting the upper layer to obtain biodiesel oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264085A (en) * | 2020-11-23 | 2021-01-26 | 淮阴工学院 | Solid base catalyst KF/Mg-Al-LDO/MCM-41 and preparation method and application thereof |
| CN112495451A (en) * | 2020-11-24 | 2021-03-16 | 大连理工大学 | Method for manufacturing solid catalyst by using laser processing technology |
| CN115475613A (en) * | 2022-09-29 | 2022-12-16 | 北部湾大学 | Modified oyster shell solid base catalyst for synthesizing biodiesel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962824A (en) * | 2006-12-01 | 2007-05-16 | 湘潭大学 | Process for preparing supported solid catalyst for use in production of bio-diesel oil |
| CN101314131A (en) * | 2008-07-09 | 2008-12-03 | 东南大学 | Preparation for modified hydrotalcite solid base catalyst for preparing biological diesel oil |
| CN103406118A (en) * | 2013-08-19 | 2013-11-27 | 太原工业学院 | Bio-diesel catalyst CaO/M-Al-O and preparation method thereof |
| CN107541234A (en) * | 2017-09-02 | 2018-01-05 | 湘潭大学 | A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite |
-
2020
- 2020-05-15 CN CN202010411407.9A patent/CN111468149B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962824A (en) * | 2006-12-01 | 2007-05-16 | 湘潭大学 | Process for preparing supported solid catalyst for use in production of bio-diesel oil |
| CN101314131A (en) * | 2008-07-09 | 2008-12-03 | 东南大学 | Preparation for modified hydrotalcite solid base catalyst for preparing biological diesel oil |
| CN103406118A (en) * | 2013-08-19 | 2013-11-27 | 太原工业学院 | Bio-diesel catalyst CaO/M-Al-O and preparation method thereof |
| CN107541234A (en) * | 2017-09-02 | 2018-01-05 | 湘潭大学 | A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite |
Non-Patent Citations (1)
| Title |
|---|
| ARIEL GUZMÁN-VARGAS ET AL: "Efficient KF loaded on MgCaAl hydrotalcite-like compounds in the transesterification of Jatropha curcas oil", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264085A (en) * | 2020-11-23 | 2021-01-26 | 淮阴工学院 | Solid base catalyst KF/Mg-Al-LDO/MCM-41 and preparation method and application thereof |
| CN112264085B (en) * | 2020-11-23 | 2022-06-14 | 淮阴工学院 | Solid base catalyst KF/Mg-Al-LDO/MCM-41 and preparation method and application thereof |
| CN112495451A (en) * | 2020-11-24 | 2021-03-16 | 大连理工大学 | Method for manufacturing solid catalyst by using laser processing technology |
| CN115475613A (en) * | 2022-09-29 | 2022-12-16 | 北部湾大学 | Modified oyster shell solid base catalyst for synthesizing biodiesel and preparation method thereof |
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