CN111468149B - Biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof - Google Patents
Biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof Download PDFInfo
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- CN111468149B CN111468149B CN202010411407.9A CN202010411407A CN111468149B CN 111468149 B CN111468149 B CN 111468149B CN 202010411407 A CN202010411407 A CN 202010411407A CN 111468149 B CN111468149 B CN 111468149B
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- 229910018516 Al—O Inorganic materials 0.000 title claims abstract description 143
- 239000003225 biodiesel Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 186
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 241000221089 Jatropha Species 0.000 claims description 38
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- 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 28
- 229960001545 hydrotalcite Drugs 0.000 claims description 28
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 28
- 239000012018 catalyst precursor Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
- 239000012684 catalyst carrier precursor Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 19
- 239000002585 base Substances 0.000 abstract description 18
- 239000003513 alkali Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 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
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 239000011698 potassium fluoride Substances 0.000 description 81
- 239000000243 solution Substances 0.000 description 47
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 23
- 239000011148 porous material Substances 0.000 description 19
- 239000011575 calcium Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006555 catalytic reaction Methods 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
- 238000005809 transesterification reaction Methods 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
- 230000001965 increasing effect Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241001048891 Jatropha curcas Species 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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 4
- 238000011160 research Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910018553 Ni—O Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- 235000019737 Animal fat Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000010794 food waste Substances 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
- 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
- 239000004179 indigotine Substances 0.000 description 1
- 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
- 229910052749 magnesium 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
- 238000002156 mixing Methods 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a 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) preparation of magnesium-aluminum composite metal oxide; (2) preparation of a modified catalyst carrier; (3) preparation of the 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 easy separation, high product quality and the like in the use process; the catalyst prepared by the invention has the advantages of less alkali dissolution, good reusability, acid resistance, water resistance and saponification resistance in the use process. The catalyst has good catalytic activity, less alkali dissolution loss, simple preparation process, abundant raw materials and low price, so the catalyst is a solid base catalyst suitable for popularization and application, and can be effectively applied to biodiesel preparation.
Description
Technical Field
The invention relates to the technical field of preparation of a solid catalyst and biodiesel synthesis, 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
Currently, the worldwide available petrochemical resources are gradually reduced, and along with the development of economy and society, the demand of human beings for petroleum energy is gradually increased, and the petrochemical resources gradually present the condition of short supply to control the emission of toxic pollutants and cancerogenic substances. The biodiesel is a renewable diesel fuel which is prepared by taking oil crops or animal fat, food waste oil and the like as raw oil through transesterification or other methods and can replace petrochemical diesel, has the advantages of being renewable, clean and the like, and has the main component of Fatty Acid Methyl Ester (FAME). The synthesis of low cost biodiesel is not only a major challenge for manufacturers, but also a great challenge for scientists and researchers.
At present, the mass production of biodiesel is mainly realized by synthesizing biodiesel through transesterification. Although the reaction efficiency is high, the separation of the products after the end of the reaction is a difficult problem 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 easily separated, 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 prior report, the grade of chemical reagent used in the preparation process of most catalysts of biodiesel is Chemical Purity (CP) or experimental reagent (LR), the preparation process has high requirements on reagent conditions, the consumption cost is high, and the experimental conditions are severe. Some catalysts have poor reusability and regenerated catalysts have high cost.
Caustic alkali such as sodium hydroxide or potassium hydroxide or solid acid catalyst is a common method for preparing biodiesel in industry, has the characteristic of high biodiesel yield, but has the defects of equipment corrosion and scaling, pipeline blockage, difficult catalyst separation and post-treatment and the like, and can cause environmental pollution to a certain extent. Thus, the supported solid base catalyst has been further developed. Patent CN106345448A reports that biodiesel is prepared by using single components such as various shell powder, active carbon, znO and the like as carrier-supported active components. Patent CN105642268A reports that a hydrotalcite-like compound is prepared from nitrate of cerium, lanthanum or lithium, calcium, magnesium and aluminum as raw materials, urea as a precipitant, and then a solid base catalyst is prepared by high-temperature roasting, but the catalyst in the prior art is complex in preparation and the yield of the product is not very high.
The Ca-Al-O, mg-Al-O and Zn-Al-O composite oxides are singly used as biodiesel catalysts, and have a certain research report that the catalytic activity sequence is as follows; ca-Al-O > Mg-Al-O > Zn-Al-O; the acid-resistant and water-resistant capability sequence is that Zn-Al-O > Mg-Al-O > Ca-Al-O is seen from two sequences, the Ca-Al-O catalyst has strong activity and fast catalytic reaction rate, but has poor acid-resistant and water-resistant capability. The requirements on raw materials are severe: the Zn-Al-O catalyst has strong acid-resistant and water-resistant capability, loose requirements on raw materials, but poor activity and slow catalytic reaction rate.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides the biodiesel solid catalyst KF/Ca-Mg-Al-O and the preparation method thereof, and the prepared catalyst has the characteristics of good activity, water resistance, acid resistance, saponification resistance, easy separation of products, 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, such as easy formation of a reaction mixture into slurry which is difficult to separate, incapability of effectively separating the products, less utilization of biodiesel and poor quality. Meanwhile, the experimental reagents used in the preparation process of the catalyst are all industrial grade, the production cost is low, and the requirements on experimental conditions are not harsh.
The invention relates to a preparation method and application of biodiesel solid catalyst KF/Ca-Mg-Al-O.
The technical scheme is as follows: in order to achieve the above purpose, the preparation method of the biodiesel solid catalyst KF/Ca-Mg-Al-O comprises the following steps:
(1) Mg (Cl) 2 ·6H 2 O and Al (Cl) 3 ·6H 2 Preparing solution A from O, stirring and adding ammonia water solution until the pH value of the solution A is 10-11, stopping adding the ammonia water solution, standing for crystallization, filtering, and drying filter residues to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite to obtain Mg-Al-O;
(2) Adding Mg-Al-O to Ca (OH) 2 Soaking 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 Ca-Mg-Al-O serving as a catalyst carrier into KF solution, soaking and 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, step (1) the Mg (Cl) 2 ·6H 2 O and Al (Cl) 3 ·6H 2 The dosage of O is respectively Mg 2+ And Al 3+ In terms of mole ratio, n (Mg 2+ ):n(Al 3+ ) =1-5:1. The stirring speed in the step (1) is 500-800r/min. Crystallizing at 80-100 ℃ for 2-4h, pouring the crystallized mixture into a buchner funnel connected with a suction filter flask for suction filtration, washing filter residues to be neutral, and drying at 80-100 ℃ for 4-6h to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 600-900 deg.c for 2-5 hr. And (3) adding ammonia water to the pH value of 10-11 in the step (1).
Step (2) the Ca (OH) 2 The concentration of the solution is 1-5wt%, and the concentration of Mg-Al-O and Ca (OH) are equal to each other 2 The solution ratio was 1:1.05g/mL. And (2) soaking for 4-6h at 20-25 ℃, drying for 4-6h at 80-100 ℃ to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O 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 10-30wt%, and the ratio of the catalyst carrier Ca-Mg-Al-O to the KF solution is 1:1.1g/mL. And (3) soaking for 12-16h at 20-25 ℃, drying for 4-6h at 80-100 ℃ to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O for 2-7h at 400-900 ℃ to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Preferably, the stirring speed in the step (1) is 600r/min; crystallizing for 3 hours at 90 ℃, then carrying out vacuum suction filtration, washing filter residues to be neutral by water, and drying for 6 hours at 80 ℃ to obtain the magnesium-aluminum hydrotalcite; the magnesium-aluminum hydrotalcite was calcined at 700 ℃ for 3 hours. Ammonia was added to a pH of 10.
Preferably, the impregnation in the step (2) is carried out at 25 ℃ for 6 hours and 80 ℃ for 6 hours, so as 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 3h.
Preferably, the impregnation in the step (3) is carried out at 25 ℃, 12h and 6h drying at 80 ℃ to obtain the catalyst precursor KF/Ca-Mg-Al-O.
The biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by the preparation method of the biodiesel solid catalyst KF/Ca-Mg-Al-O.
The invention relates to an application of a biodiesel solid catalyst KF/Ca-Mg-Al-O prepared by a preparation method of the biodiesel solid catalyst KF/Ca-Mg-Al-O in preparing biodiesel by catalysis.
The application comprises the following specific processes:
the pretreatment process is carried out on the Jatropha curcas oil before use: placing a certain amount of jatropha seed oil in a separating funnel, adding methanol to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, plugging a plug, shaking, standing, pouring out upper-layer methanol after layering, adding methanol again to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, and repeating the above operation until the acid value of the measured jatropha seed oil is less than 1mg KOH/g, so that the jatropha seed oil after being subjected to treatment is used as a raw material for preparing biodiesel.
The reaction is carried out in a single-neck flask, the reaction conditions are controlled to be methanol, pretreated jatropha seed oil (mol: mol) =14:1, and the mass of the catalyst KF/Ca-Mg-Al-O is as follows: the mass=0.04% of the pretreated jatropha seed oil, the reaction temperature is 65 ℃, and the reaction time is controlled to be 3h.
And after the reaction is finished, carrying out rotary evaporation on the reactant to remove the unreacted methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the stirring speed is controlled at 30r/min.
Placing reactants in a separating funnel, standing the catalyst and glycerin to sink at the bottom of the separating funnel, discharging the glycerin and the catalyst at the lower layer, taking an upper layer of crude biodiesel layer, adding a proper amount of distilled water, washing for multiple times to neutrality, removing a small amount of methanol residues, alkaline substances falling off in the reaction process of the solid base catalyst and the like. Adding 25% sodium sulfate water into the upper layer biodiesel layer for dehydration, shaking, centrifuging, and collecting the upper layer to obtain biodiesel. 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 adopts magnesium chloride and aluminum chloride as raw materials to prepare a composite catalyst carrier. Meanwhile, compared with a method of directly using composite metal oxide as a biodiesel catalyst, the method for loading potassium fluoride has the advantage that the yield of biodiesel is higher. The catalyst has certain acid-resistant, water-resistant and soap-resistant capacities while using Mg-Al-O as a catalyst carrier. In addition, ca (OH) is used after the preparation of the Mg-Al-O carrier is completed 2 The catalyst carrier is modified, so that the acid-resistant, water-resistant and soap-resistant capabilities are further improved, and through calcination, the SEM image shows that the catalyst carrier has a porous structure, the specific surface area is increased, and the active sites when the catalyst carrier is combined with KF are increased.
Firstly, preparing magnesium-aluminum composite metal oxide; preparing a modified catalyst carrier; preparing a catalyst; KF/Ca-Mg-Al-O solid base catalyst is prepared by coprecipitation method and isovolumetric impregnation method. Compared with the traditional homogeneous catalyst, the catalyst prepared by the invention has the characteristics of easy separation, high product quality and the like in the use process; compared with the traditional heterogeneous solid base 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 use process.
The design principle of the catalyst is to use Mg 2+ And Al 3+ Coprecipitation in alkaline environment to prepare magnesium aluminum hydrotalcite, which is formed after high temperature calcination, has pore Mg-O-Al structure and utilizes free Ca 2+ Part of Mg in the structure 2+ Displacing to form Ca-O-Al, loading KF to form Ca-O-K, calcining at high temperature to form KCaF 3 Is supported on the surface of the catalyst.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the biodiesel catalyst KF/Ca-Mg-Al-O is prepared by firstly preparing magnesium-aluminum hydrotalcite by using a mixed solution of magnesium chloride and aluminum chloride by using a coprecipitation method, then modifying the surface of the magnesium-aluminum hydrotalcite by using calcium hydroxide to generate more acid-base active centers, preparing a catalyst carrier Ca-Mg-Al-O by calcining, loading KF on the surface of the carrier by using an isovolumetric impregnation method, preparing the catalyst KF/Ca-Mg-Al-O by calcining, performing TG characterization on the catalyst and a precursor thereof, and performing alkali strength, XRD and SEM characterization on the catalyst. The characterization result shows that after KF loading and high-temperature calcination, the catalyst forms new KCaF 3 The substance is a component having strong catalytic activity.
The jatropha seed oil used in the invention is a cheap and easily available non-edible oil with high acid value, which can cause harm to human body when eaten by mistake, and the biodiesel prepared by using the jatropha seed oil as a raw material has the advantages of low cost, no sulfur, no pollution and environmental friendliness. The catalyst prepared by the invention takes the jatropha seed oil as a raw material, and researches on the reusability of the catalyst, and the catalyst still has higher catalytic activity after being reused for 7 times. The result obtained by transesterification of 4 kinds of jatropha seed oil having different acid numbers is not sensitive to the change of acid numbers. Therefore, the catalyst has better catalytic activity, less alkali dissolution loss, simple preparation process, abundant raw materials and low price, and is a solid base catalyst suitable for popularization and application, and can be effectively applied to biodiesel preparation.
The innovation point of the invention is that Ca is used 2+ Modifying the catalyst carrier, different from the former catalyst using Mg-Al-O as carrier, ca 2+ The use of (a) enables the catalyst to form KCaF 3 Enhancing the catalytic capability; the preparation method is simple, and most experimental environments can realize preparation; the catalyst can be reused for a plurality of times, can still keep higher catalytic activity, saves cost and is environment-friendly; the biodiesel and the catalyst are in different two phases, and the product is easy to separate; the catalyst has the advantages of low use proportion, relatively large particles, easy sedimentation after the reaction is finished, no slurry formed by mixing with reactants, but good catalytic effect due to a plurality of pore channels and large specific surface area.
Drawings
FIG. 1 is an XRD pattern of a solid base catalyst of Mg-Al-O, caO, KF and KF/Ca-Mg-Al-O;
FIG. 2 is an SEM spectrum of Ca-Mg-Al-O and KF/Ca-Mg-Al-O;
FIG. 3 is a schematic diagram of a KF/Ca-Mg-Al-O catalyst reproducibility use study.
Detailed description of the preferred embodiments
The invention is further described below with reference to the drawings and examples.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The specific surface area, pore canal, 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.
The duct: the surface of the catalyst pellet is provided with micropore channels.
Pore diameter: refers to the shape and size of the cells in the porous solid. The hole is in fact extremely irregular, and is generally considered to be circular and its radius represents the size of the hole.
Pore volume: the sum of all pore volumes within the catalyst.
Example 1
(1) Mg is added with 2+ And Al 3+ Calculated by mole ratio, the following components are: n (Mg) 2+ ):n(Al 3+ ) =1:1, 2.0330g Mg (Cl) 2 ·6H 2 O and 2.4143g of Al (Cl) 3 ·6H 2 O, dissolving in 300mL of deionized water to prepare solution A; slowly adding 28% (v/v, ml/ml) ammonia water solution into the solution A under stirring at 600r/min until the pH of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3h, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask, suction filtering, washing filter residues with water to pH 7, and drying at 80 ℃ for 6h to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 700 ℃ for 4 hours to obtain the Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1mL of 1wt% Ca (OH) 2 Soaking in the solution at 25 ℃ for 6 hours, and drying at 80 ℃ for 6 hours to obtain the modified catalyst carrier precursor Ca-Mg-Al-O. And roasting the modified catalyst carrier precursor Ca-Mg-Al-O for 3 hours at 600 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O.
(3) 2g of catalyst carrier Ca-Mg-Al-O is taken and added into 2.2mL of 10wt% KF solution, immersed for 12h at 25 ℃, and dried for 4h at 100 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O. Calcining the catalyst precursor KF/Ca-Mg-Al-O at 400 ℃ for 7h to obtain the biodiesel catalyst KF/Ca-Mg-Al-O, which is called as a catalyst S 1 。
The specific method for synthesizing the biodiesel by catalyzing the KF/Ca-Mg-Al-O solid base catalyst is as follows:
the pretreatment process is carried out on the Jatropha curcas oil before use: placing a certain amount of jatropha seed oil in a separating funnel, adding methanol to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, plugging a plug, shaking, standing, pouring out upper-layer methanol after layering, adding methanol again to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, and repeating the above operation until the acid value of the measured jatropha seed oil is less than 1mg KOH/g, so that the jatropha seed oil after being subjected to treatment is used as a raw material for preparing biodiesel.
The reaction was carried out in a single-neck flask, i.e. methanol: pretreated jatropha seed oil (mol: mol) =14:1, reaction temperature was controlled at 65 ℃, catalyst: pretreated jatropha seed oil (mass ratio) =0.04%, reaction time was controlled to 3h.
After the reaction is finished, pouring the reactant into a pear-shaped bottle for rotary evaporation, removing unreacted complete methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30r/min.
Placing the reactant in a separating funnel, standing, discharging the glycerin and the catalyst at the lower layer, taking the crude biodiesel layer at the upper layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate water into the upper layer biodiesel layer for dehydration, shaking, centrifuging, and collecting the upper layer to obtain biodiesel.
Example 2
(1) Mg is added with 2+ And Al 3+ Calculated by mole ratio, the following components are: n (Mg) 2+ ):n(Al 3+ ) =3:1, 6.0990g Mg (Cl) 2 ·6H 2 O and 2.4143g of Al (Cl) 3 ·6H 2 O, dissolving in 300mL of deionized water to prepare solution A; slowly adding 28% (v/v, ml/ml) ammonia water solution into the solution A under stirring at 600r/min until the pH of the solution A is 10.5, stopping adding the ammonia water solution, standing, crystallizing at 100deg.C for 2 hr, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask, suction filtering, washing the filter residue with water to pH 7, and drying at 90deg.C for 5 hr to obtain magnesium aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 600 ℃ for 5 hours to obtain the Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1mL of 3wt% Ca (OH) 2 Soaking in the solution at 22 ℃ for 5h, and drying at 90 ℃ for 5h to obtain the modified catalyst carrier precursor Ca-Mg-Al-O. Calcining the modified catalyst carrier precursor Ca-Mg-Al-O for 3.5h at 700 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O.
(3) 2g of catalyst carrier Ca-Mg-Al-O is taken and added into 2.2mL of 20wt% KF solution, the catalyst carrier is immersed for 14h at 22 ℃ and dried for 5h at 90 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O. Calcining the catalyst precursor KF/Ca-Mg-Al-O at 600 ℃ for 5 hours to obtain the biodiesel catalyst KF/Ca-Mg-Al-O, which is called as a catalyst S 2 。
The specific method for synthesizing the biodiesel by catalyzing the KF/Ca-Mg-Al-O solid base catalyst is as follows:
the pretreatment process is carried out on the Jatropha curcas oil before use: placing a certain amount of jatropha seed oil in a separating funnel, adding methanol to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, plugging a plug, shaking, standing, pouring out upper-layer methanol after layering, adding methanol again to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, and repeating the above operation until the acid value of the measured jatropha seed oil is less than 1mg KOH/g, so that the jatropha seed oil after being subjected to treatment is used as a raw material for preparing biodiesel.
The reaction is carried out in a single-neck flask, namely, methanol is pretreated jatropha seed oil (mol: mol) =14:1, the reaction temperature is controlled at 65 ℃, and the catalyst: pretreated jatropha seed oil (mass ratio) =0.04%, reaction time was controlled to 3h.
After the reaction is finished, pouring the reactant into a pear-shaped bottle for rotary evaporation, removing unreacted complete methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30r/min.
Placing the reactant in a separating funnel, standing, discharging the glycerin and the catalyst at the lower layer, taking the crude biodiesel layer at the upper layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate water into the upper layer biodiesel layer for dehydration, shaking, centrifuging, and collecting the upper layer to obtain biodiesel.
XRD patterns of KF, caO, mg-Al-O and KF/Ca-Mg-Al-O catalysts produced in this example are shown in FIG. 1. It can be observed in XRD patterns of solid base catalysts of Mg-Al-O, caO, KF and KF/Ca-Mg-Al-O that after modification with Ca, the corresponding peak of Mg-Al-O disappears at 65 DEG and the broad peak of Mg-Al-O disappears at about 37 DEG, and a new diffraction peak is formed at about 55 DEG, and 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 as a catalyst carrier with Mg-Al-O by calcination at high temperature. The characteristic diffraction peak of KF carried by the impregnation method disappeared, and it was confirmed that KF was not simply carried on the surface of the catalyst support and a new diffraction peak was generated at 13℃so that KF formed a catalytically active material KCaF with the catalyst support after calcination at high temperature 3 。
SEM spectra of Ca-Mg-Al-O and KF/Ca-Mg-Al-O generated in this example are shown in FIG. 2. FIGS. 2 (a) and 2 (b) are catalyst supports calcined at 700 ℃. SEM of Ca-Mg-Al-O and catalyst KF/Ca-Mg-Al-O. The surface of the catalyst KF/Ca-Mg-Al-O after being loaded with KF has a larger particle structure, and the particle surface has a lamellar structure which is possibly caused by the loading of KF, which can explain the phenomenon that the specific surface area of the catalyst is slightly reduced after being loaded. And the solid surface has a porous structure, which means that pore channels appear in the catalyst in the preparation process, so that the catalyst can be better combined with reactants to provide better catalytic effect. It is further illustrated that there is an interaction between the supported KF and the support, not a simple support on the surface, but the KF forms a new material KCaF with CaO after calcination 3 XRD analysis results were verified. Furthermore, it is possible to provide a device for the treatment of a disease. The difference between the FIG. 2 (a) and the FIG. 2 (b) of the invention can obviously observe that the porous structure appears in b, but does not appear in a, and the catalyst of the invention has good catalytic effect due to the large number of pores and large specific surface area by combining with the Table 1. Because of the necessary conditions for the mutual collision reaction between the reactant molecules to proceed in a chemical reaction. Due to the increase of the specific surface area, the occurrence of pore channels improves the contact and collision opportunity of the reaction raw materials and the surface of the catalyst, and can improve the catalytic efficiency of the reaction.
Example 3
(1) Mg is added with 2+ And Al 3+ Calculated by mole ratio, the following components are: n (Mg) 2+ ):n(Al 3+ ) =5:1, 10.1650g Mg (Cl) 2 ·6H 2 O and 2.4143g of Al (Cl) 3 ·6H 2 O, dissolving in 300mL of deionized water to prepare solution A; slowly adding 28% (v/v, ml/ml) ammonia water solution into the solution A under stirring at 600r/min until the pH value of the solution A reaches 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 flask, suction filtering, washing filter residues to pH 7, and drying at 100 ℃ for 4 hours to obtain magnesium aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 900 ℃ for 2 hours to obtain the Mg-Al-O.
(2) 2g of Mg-Al-O were added to 2.1mL of 5wt% Ca (OH) 2 Immersing in the solution at 20 ℃ for 4 hours, and drying at 100 ℃ for 4 hours to obtain the modified catalyst carrier precursor Ca-Mg-Al-O. Calcining 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) 2g of catalyst carrier Ca-Mg-Al-O is taken and added into 2.2mL of 30wt% KF solution, immersed for 16h at 20 ℃, and dried for 6h at 80 ℃ to obtain catalyst precursor KF/Ca-Mg-Al-O. Calcining the catalyst precursor KF/Ca-Mg-Al-O for 2h at 900 ℃ to obtain the biodiesel catalyst KF/Ca-Mg-Al-O, which is called as a catalyst S 3 。
The specific method for synthesizing the biodiesel by catalyzing the KF/Ca-Mg-Al-O solid base catalyst is as follows:
the pretreatment process is carried out on the Jatropha curcas oil before use: placing a certain amount of jatropha seed oil in a separating funnel, adding methanol to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, plugging a plug, shaking, standing, pouring out upper-layer methanol after layering, adding methanol again to ensure that the mass-to-methanol volume ratio (g: mL) =1:2.5 of the jatropha seed oil, and repeating the above operation until the acid value of the measured jatropha seed oil is less than 1mg KOH/g, so that the jatropha seed oil after being subjected to treatment is used as a raw material for preparing biodiesel.
The reaction is carried out in a single-neck flask, namely, methanol, pretreated jatropha seed oil (mol: mol) =14:1, the reaction temperature is controlled at 65 ℃, the catalyst, pretreated jatropha seed oil (mass ratio) =0.04%, and the reaction time is controlled at 3h.
After the reaction is finished, pouring the reactant into a pear-shaped bottle for rotary evaporation, removing unreacted complete methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30r/min.
Placing the reactant in a separating funnel, standing, discharging the glycerin and the catalyst at the lower layer, taking the crude biodiesel layer at the upper layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate water into the upper layer biodiesel layer for dehydration, shaking, centrifuging, and collecting the upper layer to obtain biodiesel.
Comparative example 1
(1) Mg is added with 2+ And Al 3+ Calculated by moleThe ratio is as follows: n (Mg) 2+ ):n(Al 3+ ) =3:1, 6.0990g Mg (Cl) 2 ·6H 2 O and 2.4143g of Al (Cl) 3 · . 6H 2 O, dissolving in 300mL of deionized water to prepare solution A; slowly adding 28% (v/v, ml/ml) ammonia water solution into the solution A under stirring at 600r/min until the pH of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3h, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask, suction filtering, washing filter residues with water to pH 7, and drying at 80 ℃ for 6h to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 700 ℃ for 4 hours to obtain the Mg-Al-O.
(2) 2g of catalyst carrier Mg-Al-O is taken and added into 2.2mL of 20wt% KF solution, immersed for 12h at 25 ℃, dried for 6h at 80 ℃ to obtain a catalyst precursor D 1 . Roasting the catalyst precursor at 600 deg.c for 5 hr to obtain biodiesel catalyst, named catalyst D 1 。
Catalyst D 1 The specific method for catalytic synthesis of biodiesel was the same as in example 2.
Comparative example 2
(1) Mg is added with 2+ And Al 3+ Calculated by mole ratio, the following components are: n (Mg) 2+ ):n(Al 3+ ) =3:1, 6.0990g Mg (Cl) 2 ·6H 2 O and 2.4143g of Al (Cl) 3 ·6H 2 O, dissolving in 300mL of deionized water to prepare solution A; slowly adding 28% (v/v, ml/ml) ammonia water solution into the solution A under stirring at 600r/min until the pH of the solution A is 10, stopping adding the ammonia water solution, standing, crystallizing at 90 ℃ for 3h, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask, suction filtering, washing filter residues with water to pH 7, and drying at 80 ℃ for 6h to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 700 ℃ for 4 hours to obtain the Mg-Al-O.
(2) 2g of Mg-Al-O was added to 2.1mL of 3wt% Ca (OH) 2 Soaking in the solution at 25deg.C for 6 hr, and drying at 80deg.C for 6 hr. Roasting at 700 deg.c for 3 hr to obtain biodiesel catalyst, named catalyst D 2 。
Catalyst D 2 Specific method for catalytic synthesis of biodieselExample 2.
Comparative example 3 was the same as in example 2 of the present invention except that 2g of Mg-Al-O was added to 2.1mL of 7wt% Ca (OH) in step (2) 2 A solution.
Comparative example 4 was the same as in example 2 of the present invention except that 2g of catalyst support Ca-Mg-Al-O was taken in step (3) and added to 2.2mL of 40wt% KF solution.
Comparative example 5 was a CaO-ZnO catalyst prepared by the coprecipitation method in the "Studies on calcium-based solid base catalysts for the preparation of biodiesel" published by the university of Hebei industries, inc. of the open-hand published in 2017.
Comparative example 6 preparation of CaO/ZrO by template method published in petrochemical industry, volume 2015, 43, 7 th, 774-778, page Liu Liuchen, etc 2 CaO/ZrO prepared in biodiesel synthesis by rapeseed oil catalysis by catalyst 2 A catalyst.
The catalyst used in comparative example 7 was the catalyst of example 2, except that the raw material used in the process of producing biodiesel was waste cooking oil (and the same pretreatment process as in example 2 was used).
BET analysis was performed on the catalysts prepared in examples 1 to 3 and comparative examples 1 to 6 described above and GC analysis was performed on biodiesel prepared therefrom, and biodiesel productivity was calculated, and the results are shown in Table 1.
Table 1 physical properties of catalyst and productivity of biodiesel prepared therefrom
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 pore channels are formed by calcining the magnesium-aluminum hydrotalcite at high temperature to obtain Mg-Al-O, and the pore channels are slightly smaller when Ca is used for modification and KF is loaded. However, the biodiesel yields of examples 1-3 were higher than D 1 This is due to Ca 2+ Is present to replace part of the Mg in the Mg-Al-O lattice 2+ And Al 3+ To enhance its alkalinity as biodieselThe yield is higher. And D is 2 It is because it does not carry the catalytically active component KF and does not have very good catalytic properties.
From S in Table 1 2 And D 1 And D 3 It can be seen that Ca was increased under otherwise identical conditions 2+ The amount of Ca does not increase the yield of the biodiesel 2+ The presence of (2) can increase its basicity but too much, the surface will be covered by excess 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.
From S in Table 1 2 And D 2 And D 4 It can be seen that KF is a necessary substance effective in improving catalytic activity, but too much addition does not increase biodiesel productivity all the time because KF already occupies all the surface active sites and forms a catalytically active material KCaF after calcination at high temperature 3 While a further increase in KF cannot bind to the active site, the binding site is already saturated, and since it cannot bind, increasing KF will cause a decrease in the amount of catalytically active species in a certain amount of catalyst.
From S in Table 1 2 And D 5 And D 6 It can be seen that the catalyst surface structure of the invention is advantageous, and when the specific surface area, pore diameter and pore volume of the catalyst are different greatly, the larger specific surface area can be more beneficial to catalytic reaction.
In addition, the catalyst of example 2 was subjected to an alkali strength test, which comprises the steps of: fresh 5.0g of catalyst was taken, 25.0mL of cyclohexane was added, shaking was performed for 30min, then 2-3 drops of a benzene solution containing 0.1% phenolphthalein indicator were added, and after adsorption equilibrium was reached, the color change on the catalyst surface was observed. The indicator is phenolphthalein (pK) a Value 9.8), indigo carmine (pK a Value 12.2), 2, 4-dinitroaniline (pK a Value 15.0), 4-nitroaniline (pK a Value 18.4). After seven times of use, the surface color of the catalyst is not changed obviously, which indicates that the alkali strength is not changed greatly.
The results of the reusability test of the catalyst in example 2 are shown in fig. 3, and the steps are as follows: after the reaction, separating the catalyst by adopting a centrifugal separation method from the mixture of the catalyst and the glycerin discharged from the lower layer of the separating funnel after standing, heating, refluxing and stirring the used catalyst for 1h at 50 ℃ by using 50mL of methanol, filtering, and then drying in vacuum for 2h at 120 ℃ to obtain the regenerated catalyst. The regenerated catalyst obtained is used for further catalyzing transesterification (prepared by biodiesel in the same example 2), and the catalyst after the reaction is ended is regenerated repeatedly according to the steps. After 7 times, the biodiesel yield generally decreased, with the first catalyst preparation in fig. 3 yielding 98.51%, but after 7 uses the biodiesel yield was still 88.23%, and the 7 repetitions were only reduced by 10.28%. The catalyst has good reusability, and meanwhile, products and raw materials are easy to separate, and the product quality is good. In addition, the performance of KF/Ca-Mg-Al-O and some existing catalysts in terms of reusability in the invention is examined by adopting the method, and the specific results are shown in Table 2.
TABLE 2 differentiation of different catalysts in terms of recyclability
As is clear from Table 2, the KF/Ca-Mg-Al-O catalyst is the catalyst prepared in example 2 of the present invention, ba (OH) 2 The catalyst was "Ba (OH) published in Jiang Nada science Pan Lishuang 2017 2 Research on biodiesel production by catalytic methyl esterification of castor oil "catalyst in the" Shuoshi paper. K (K) 2 CO 3 the/Al-Ni-O catalyst is Wu Xiaoni and the like in the paper "solid alkali K" published on pages 61-63 at 24 th of 24 th Vol.24 of 2016 of Industrial catalyst 2 CO 3 Al-Ni and K 2 CO 3 The catalyst prepared in the preparation of biodiesel by Al-Ni-O catalysis. The KF/MMT catalyst is Fan Fenglan and the like in the paper "KF/MMT solid base catalyst" published on pages 56-59 of 10 th period of volume 38 of oil chemical industry 2013The catalyst prepared in the preparation and catalysis of transesterification reaction. NaOH and H 2 SO 4 Is a catalyst prepared by Chen Ying and the like in the research on the process for preparing biodiesel from homogeneously catalyzed waste cooking oil in the paper published on 415-420 pages in 5 of 26 th edition of 9 th month of 2008 of petroleum technology and application. Compared with the catalyst, the catalyst has the advantages of repeated times and biodiesel yield after repeated use. The homogeneous catalyst is difficult to realize in terms of recycling, the recycling can lead to high cost, and the used acid or alkali can remain in the product biodiesel, so that the quality of the biodiesel is low.
In comparative example 7 in Table 2, the catalyst of example 2 of the present invention was excellent in recyclability of waste oils and fats, although the raw materials were different. The jatropha seed oil raw material is easy to obtain, the cost is low, the catalyst is more suitable for being used as a raw material for producing biodiesel, waste catering oil needs to be purchased at each designated site of waste oil, the waste catering oil is often in a dispersed state, the single purchasing site quantity is less, the collection is troublesome, a large amount of manpower and material resources are required to be consumed, and the comprehensive cost of the raw material is relatively high, so that the catalyst can be used for preparing low-cost biodiesel by catalyzing the jatropha seed oil, and the catalyst is superior to a homogeneous catalyst in reusability.
By contrast, the catalyst has more repeated times, and the biodiesel yield is not obviously reduced after repeated use. Therefore, the catalyst prepared by the invention has better reusability than the catalyst, and the production cost can be saved when the catalyst is applied to industrial production.
The catalyst of example 2 was subjected to acid resistance recycling test, which comprises the following steps: four kinds of soybeans having an acid value 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, pretreated jatropha seed oil (mol: mol) =14:1, the reaction temperature is controlled at 65 ℃, the catalyst, pretreated jatropha seed oil (mass ratio) =0.04%, and the reaction time is controlled at 3h. After the reaction is finished, pouring the reactant into a pear-shaped bottle for rotary evaporation, removing unreacted complete methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is controlled at 30r/min. Placing the reactant in a separating funnel, standing, discharging the glycerin and the catalyst at the lower layer, taking the crude biodiesel layer at the upper layer, adding a proper amount of distilled water, washing for multiple times, and washing to be neutral. Adding 25% sodium sulfate water into the upper layer biodiesel layer for dehydration, shaking, centrifuging, and collecting the upper layer to obtain biodiesel. The biodiesel yield of the reaction product is measured and is respectively 97.22 percent, 96.18 percent, 95.36 percent and 94.55 percent, and the yield is reduced by 2.67 percent, thus proving that the catalyst has good acid resistance.
Example 4
Example 4 was prepared in the same manner as example 2, except that: crystallizing at 80 ℃ for 4 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask, performing suction filtration, washing filter residues to be neutral, drying at 80 ℃ for 6 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at 600 ℃ for 5 hours; step (1) ammonia is added to the pH of solution A to 11. And (2) dipping at 20 ℃ for 6 hours, drying at 80 ℃ for 6 hours to obtain a modified catalyst carrier precursor Ca-Mg-Al-O, and roasting the modified catalyst carrier precursor Ca-Mg-Al-O at 600 ℃ for 4 hours to obtain the biodiesel catalyst carrier Ca-Mg-Al-O. And (3) soaking for 16h at 20 ℃, drying for 6h at 80 ℃ to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O for 7h at 400 ℃ to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Example 5
Example 5 was prepared in the same manner as example 2 except that: crystallizing in the step (1) at 100 ℃ for 2 hours, pouring the crystallized mixture into a Buchner funnel connected with a suction filter flask for suction filtration, washing filter residues with water to be neutral, drying at 100 ℃ for 4 hours to obtain magnesium-aluminum hydrotalcite, and roasting the magnesium-aluminum hydrotalcite at 900 ℃ for 2 hours. And (2) soaking for 4 hours at 25 ℃, drying for 4 hours 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 3 hours at 900 ℃ to obtain the biodiesel catalyst carrier Ca-Mg-Al-O. And (3) soaking for 12 hours at 25 ℃, drying for 4 hours at 100 ℃ to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O for 2 hours at 900 ℃ to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
Claims (4)
1. The application of a biodiesel solid catalyst KF/Ca-Mg-Al-O in the catalytic preparation of biodiesel comprises the following specific processes:
the reaction condition is controlled to be that the molar ratio of methanol to pretreated jatropha seed oil is 14:1, the mass of catalyst KF/Ca-Mg-Al-O is 0.04% of the mass of pretreated jatropha seed oil, the reaction temperature is controlled to be 65 ℃, and the reaction time is controlled to be 3 h; after the reaction is finished, the reactants are subjected to rotary evaporation to remove the unreacted complete methanol in the product, wherein the pressure is 0.03MPa, the temperature is 55 ℃, and the rotating speed is 30 r/min; pouring reactants into a separating funnel, standing, removing the glycerin and the catalyst at the lower layer, taking an upper layer of crude biodiesel layer, adding distilled water, washing to be neutral, taking the upper layer of biodiesel layer, adding 25% sodium sulfate water for dehydration, shaking, centrifuging, and taking the upper layer to obtain biodiesel;
the preparation method of the biodiesel solid catalyst KF/Ca-Mg-Al-O comprises the following steps:
(1) Mg (Cl) 2 ·6H 2 O and Al (Cl) 3 ·6H 2 Preparing solution A from O, stirring, adding ammonia water solution into the solution A, standing, crystallizing, filtering, and drying filter residues to obtain magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite to obtain Mg-Al-O;
(2) Adding Mg-Al-O to Ca (OH) 2 Soaking 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, soaking and drying to obtain a catalyst precursor KF/Ca-Mg-Al-O, and roasting the catalyst precursor KF/Ca-Mg-Al-O at a high temperature to obtain a biodiesel catalyst KF/Ca-Mg-Al-O;
step (1) the Mg (Cl) 2 ·6H 2 O and Al (Cl) 3 ·6H 2 The dosage of O is respectively Mg 2+ And Al 3+ In terms of mole ratio, n (Mg 2+ ):n(Al 3+ )=1-5:1；
Step (2) the Ca (OH) 2 The concentration of the solution is 1-5wt%, and the concentration of Mg-Al-O and Ca (OH) 2 The solution proportion is 1:1.05 g/mL;
the concentration of the KF solution in the step (3) is 10-30wt%, and the ratio of the catalyst carrier Ca-Mg-Al-O to the KF solution is 1:1.1g/mL.
2. The use according to claim 1, wherein the crystallization in step (1) is carried out at 80-100 ℃, 2-4h are crystallized, the crystallized mixture is poured into a buchner funnel connected with a suction filter bottle for suction filtration, filter residues are washed to be neutral, and 4-6h are dried at 80-100 ℃ to obtain the magnesium-aluminum hydrotalcite; roasting the magnesium-aluminum hydrotalcite at 600-900 ℃ for 2-5 h; and (3) adding ammonia water into the solution A in the step (1) to enable the pH value to be 10-11.
3. The use according to claim 1, wherein the impregnation in step (2) is performed at 20-25 ℃ for 4-6 hours, drying at 80-100 ℃ for 4-6h to obtain a modified catalyst support precursor Ca-Mg-Al-O, and calcining at 600-900 ℃ the modified catalyst support precursor Ca-Mg-Al-O for 3-4h to obtain the biodiesel catalyst support Ca-Mg-Al-O.
4. The use according to claim 1, wherein the impregnation in step (3) is carried out at 20-25 ℃ for 12-16h, drying at 80-100 ℃ for 4-6h to obtain a catalyst precursor KF/Ca-Mg-Al-O, and calcining the catalyst precursor KF/Ca-Mg-Al-O at 400-900 ℃ for 2-7h to obtain the biodiesel catalyst KF/Ca-Mg-Al-O.
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