CN113385198B - Ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof - Google Patents
Ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical class [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011973 solid acid Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 14
- 239000002253 acid Substances 0.000 claims abstract description 64
- 239000011148 porous material Substances 0.000 claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003225 biodiesel Substances 0.000 claims abstract description 35
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 33
- 239000003549 soybean oil Substances 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 11
- 238000009997 thermal pre-treatment Methods 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000693 micelle Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 241000894007 species Species 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003930 superacid Substances 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- -1 polybutylene Polymers 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000002336 sorption--desorption measurement Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
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- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material, which is prepared by dissolving a block copolymer nonionic surfactant, organic carboxylic acid, inorganic acid, a zirconium source and an aluminum source in a mixed solution of deionized water and absolute ethyl alcohol, sequentially carrying out thermal pretreatment of a solvent, volatilization treatment of the solvent, thermal polymerization treatment and roasting treatment to obtain an ordered mesoporous zirconium-aluminum composite oxide, and using the ordered mesoporous zirconium-aluminum composite oxide as a carrier to carry sulfuric acid groups. The solid acid material prepared by the invention has a regular and ordered mesoporous pore channel structure, a larger specific surface area and pore volume, higher structural stability, and adjustable acid amount on the surface of the mesoporous pore wall, acid center type, distribution and strength, and can be used for catalyzing the transesterification reaction of soybean oil and methanol to show excellent biodiesel yield, catalytic stability and regeneration performance.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic porous solid acid catalytic materials, and relates to a sulfated zirconia-based composite metal oxide solid acid material and a preparation method thereof. The composite metal oxide solid acid material has a regular and ordered mesoporous pore structure, a larger specific surface area and pore volume, and higher structural stability, and the acid amount on the surface of the pore wall, the type, distribution and strength of acid centers are adjustable, so that the composite metal oxide solid acid material can be used for catalyzing the transesterification reaction of soybean oil and methanol to synthesize biodiesel.
Background
As a renewable energy source, the biodiesel can partially replace the traditional fossil fuel so as to effectively relieve the contradiction between the increase of the demand of the current fossil fuel and the shortage of energy.
Converting triglyceride and fatty acid in animal and vegetable oil or waste cooking oil into alkane monoester compound through ester exchange reaction and esterification reaction (commonly used method for synthesizing biodiesel oil at presentSci. Total. Environ., 2021, 768, 144856；Bioresource Technol., 2021, 326, 124772). The basic catalyst is susceptible to deactivation by free fatty acids and water in fats and oils, although it can effect transesterification under mild conditions (Chem. Eng. J., 2019, 364, 111；Chem. Eng. J., 2021, 408, 127277). On the contrary, the acid catalyst can simultaneously convert triglyceride and free fatty acid into corresponding fatty acid monoester, complete the synthesis of the biodiesel and show higher application advantages.
Compared with the traditional liquid acid catalyst, the solid acid catalyst has the advantages of high catalytic activity, easy separation, little pollution, no corrosion to equipment, regeneration and recycling, and the like, and becomes an important way for realizing a new environment-friendly process for preparing biodiesel (theChem. Eng. J., 2019, 364, 111；Chem. Eng. J., 2021, 408, 127277)。
Among various solid acid catalysts, sulfated metal oxides, particularly sulfated zirconia, have a wide application prospect in catalytic reactions such as alkylation, isomerization, acylation, cyclization, cracking, condensation, esterification and transesterification due to their excellent super strong acidity (seeProg. Chem., 2011,23, 860；J. Mol. Catal. A-Chem2005, 237, 93), has become a hotspot of research in the field of solid acid catalysis.
A great deal of experiment and theoretical calculation results show that the crystal phase structure, the specific surface area and the surface electronic property of the zirconia carrier directly influence the coordination structure and the bonding action between the zirconia carrier and a sulfuric acid group, and further influence the surface acid amount, the acid center type, the distribution and the strength of the obtained material (theJ. Phys. Chem. C, 2007, 111, 18731；Chem. Eng. J., 2019, 364, 111). In addition to this, the present invention is,for a complete and sustainable catalytic reaction, the increase of the pore diameter of the catalyst and the optimization of the pore structure are beneficial to increasing the diffusion rate of reaction molecules and simultaneously increasing the contact probability of reaction active sites and the reaction molecules, and a more ideal heterogeneous catalytic effect is expected to be achieved.
However, the mesoporous zirconia carrier prepared by the conventional method is often disordered 'worm-shaped pore' structure, and shows the defects of poor porosity, low specific surface area, small pore diameter, easy occurrence of crystal phase transformation under heating and the like, so that the solid acid material obtained after loading sulfuric acid groups generally has the problems of low acid content, poor structural stability, easy inactivation due to loss of active components or formation of carbon deposition in the reaction process and the like, and the practical catalytic application of the mesoporous zirconia carrier is severely limited.
Therefore, how to develop the zirconia-based carrier material which has high stability of a pore channel structure, large specific surface area and pore diameter and strong bonding effect with sulfuric acid groups while introducing ordered mesopores to improve the diffusion rate of reactants and products through a simple and easily-repeated preparation process realizes the stable immobilization of a large amount of sulfuric acid groups, and simultaneously modulates the type, distribution and strength of acid centers on the surface of the obtained solid acid material, thereby having important practical application value for the production of biodiesel.
Disclosure of Invention
The invention aims to provide an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material and a preparation method thereof, wherein a dissolving heat assisted volatilization induction self-assembly method is adopted, aluminum atoms are efficiently and uniformly doped, the mesostructure order and stability of the obtained zirconium-aluminum composite oxide material are improved, the specific surface area and the aperture are increased, meanwhile, the electronic property of the surface of a pore wall is modulated, and the pore wall is used as a carrier to fixedly carry sulfuric acid groups, so that the prepared mesoporous pore channel solid acid catalyst has the advantages of regular and ordered structure, large specific surface area and aperture, high structure stability, adjustable surface acid amount, acid center type, distribution and strength, and can be used for efficiently and stably producing biodiesel through the transesterification reaction of soybean oil and methanol.
The ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material is prepared by the following method:
1) dissolving inorganic acid, organic carboxylic acid and a block copolymer nonionic surfactant in a mixed solution of deionized water and absolute ethyl alcohol according to a molar mixture ratio of zirconium source, aluminum source, organic carboxylic acid, inorganic acid, deionized water, absolute ethyl alcohol and block copolymer nonionic surfactant of = (10-100): (0-40): (10-120): (50-300): 1000-3000): 1, slowly adding the zirconium source and the aluminum source, and stirring to obtain a clear solution;
2) placing the clear solution in a sealed high-pressure reaction kettle, and carrying out solvent thermal pretreatment for 5-24 hours at the temperature of 60-120 ℃ to obtain a surfactant composite micelle solution wrapping zirconium and aluminum hydroxyl species;
3) volatilizing the surfactant composite micelle solution to be dry, heating to 100-180 ℃, and carrying out thermal polymerization treatment for 24-48 h to obtain an ordered mesoporous zirconium-aluminum composite oxide wrapping the surfactant micelle;
4) roasting in the air to remove the surfactant micelle existing on the ordered mesoporous zirconium-aluminum composite oxide wrapping the surfactant micelle to obtain the ordered mesoporous zirconium-aluminum composite oxide;
5) and placing the ordered mesoporous zirconium-aluminum composite oxide in a sulfuric acid solution for dipping treatment, and then roasting at 300-650 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
In the preparation method, the block copolymer type nonionic surfactant is used as an organic template machine for guiding a mesoporous structure, and is a nonionic block copolymer with a structural formula of EOnPOmEOn, EOnBOmEOn or EOnPS, polyethylene oxide is used as a hydrophilic block, polypropylene oxide, polybutylene oxide or polystyrene is used as a hydrophobic block, wherein n = 10-200, and m = 5-120.
In the structural formula, EO represents ethylene oxide, PO represents propylene oxide, BO represents butylene oxide, and PS represents polystyrene.
In the preparation method, the zirconium source is one of zirconium oxychloride, zirconium isopropoxide, zirconium acetate or zirconium nitrate, or a mixture of several of the zirconium oxychloride, the zirconium isopropoxide, the zirconium acetate or the zirconium nitrate in any proportion.
In the preparation method, the aluminum source is one of aluminum isopropoxide, aluminum tert-butoxide, aluminum isobutanolate, aluminum nitrate or aluminum chloride, or a mixture of several of the aluminum sources in any proportion.
In the preparation method, the inorganic acid is hydrochloric acid, nitric acid or phosphoric acid.
In the preparation method, the organic carboxylic acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
Wherein, the step 1) can be carried out at normal temperature or slightly higher than normal temperature, so as to obtain clear solution for solvothermal pretreatment.
Further, it is preferable to stir at a temperature of 20 to 45 ℃ to obtain a clear solution for solvothermal pretreatment. Generally, the clear solution can be obtained after stirring for 2-5 hours.
In the step 3), the surfactant composite micelle solution is preferably subjected to volatilization treatment at 45 to 80 ℃ in an open state.
Generally, the heat polymerization treatment can be performed in the next step by volatilizing the mixture for 6 to 24 hours in the open state.
In the step 4), the ordered mesoporous zirconium-aluminum composite oxide coating the surfactant micelle is preferably calcined in air at 400 to 750 ℃ to remove the surfactant micelle.
Preferably, the roasting time is 3-5 h.
In the step 5), preferably, the ordered mesoporous zirconium-aluminum composite oxide is immersed in a sulfuric acid solution with a concentration of 0.1-2 mol/L according to a solid/liquid volume ratio of (0.05-1) to 1.
Further, the ordered mesoporous zirconium-aluminum composite oxide is preferably subjected to dipping treatment for 10 to 60min in a sulfuric acid solution under stirring.
The method has the advantages that through the dissolving thermal pretreatment of the absolute ethyl alcohol solution in which the segmented copolymer nonionic surfactant, the inorganic acid, the organic carboxylic acid, a small amount of deionized water and zirconium and aluminum precursors are dissolved, the forward progress of the hydrolysis reaction of the zirconium and aluminum precursors in the synthetic solution is promoted while the critical micelle concentration of the surfactant is reduced; by adjusting the temperature and time of the thermal pretreatment of the solvent and combining the proper introduction of the organic carboxylic acid coordination agent and the deionized water, the polymerization rate, the hydroxyl content and the hydrogen bond interaction between the hydrophilic block of the organic template micelle of zirconium and aluminum hydroxyl species in a synthesis system are regulated and controlled, and the formation of the surfactant composite micelle solution wrapping the zirconium and aluminum hydroxyl species is promoted.
In the subsequent solvent volatilization treatment process, along with the gradual reduction of the solvent amount, the surfactant composite micelle is gradually gathered and accumulated to be assembled into an ordered two-dimensional hexagonal mesoporous structure with more stable thermodynamics. Then, regulating and controlling the polymerization degree and the crosslinking degree of zirconium and aluminum hydroxyl species wrapping the surface of the organic template agent micelle by regulating the temperature and time of thermal polymerization treatment, and promoting the polymerization crosslinking of the zirconium and aluminum hydroxyl species in the inorganic framework on the premise that the surfactant composite micelle plays a role in supporting the mesoporous framework and preventing the framework from collapsing in the thermal polymerization process to obtain the mesoporous pore wall containing the Zr-O-Al bond of the framework.
And finally, removing the organic template agent existing in the mesoporous pore channel by roasting to obtain the zirconium-aluminum composite oxide with the ordered mesoporous structure, and taking the zirconium-aluminum composite oxide as a carrier for the immobilization of sulfate groups.
In the preparation method, the specific surface area, pore volume, pore diameter and surface electronic property of the ordered mesoporous zirconium-aluminum composite oxide are regulated and controlled by regulating the preparation conditions and combining with the modulation of the introduced amount of aluminum, so that the regulation and control of the surface acid amount, acid type, distribution and strength of the sulfated zirconium-aluminum composite oxide solid acid material are realized.
The preparation method of the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material is simple and easy to implement, the reproducibility is high, the prepared solid acid material has a regular and ordered two-dimensional hexagonal mesoporous pore channel structure, high structural stability, large specific surface area and mesoporous pore diameter, zirconium and aluminum atoms in the pore wall can be uniformly dispersed at the atomic level, and the surface acidity is adjustable.
Through determination, the specific surface area of the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is 150-420 m 2 Per gram, pore volume 0.3-1.2 cm 3 The pore diameter is 4.0-18.0 nm, the molar ratio of zirconium atoms to aluminum atoms in the pore walls can be adjusted within the range of 0.1-10, and the acid amount, the acid density, the ratio of B acid centers to L acid centers and the content of super acid centers on the surface of the pore walls can be respectively 0.1-5.2 mmol/g, 0.0001-0.018 mmol/m 2 0.01 to 2.1 and 0 to 0.8 mmol/g.
The ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is used as a catalyst, and shows extremely high catalytic activity, stability and regenerable reusability.
The ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is used as a catalyst in the transesterification reaction of soybean oil and methanol to synthesize biodiesel, the complete conversion of the soybean oil can be realized under the low temperature condition of 100 ℃, and the yield of the biodiesel is not lower than 99.0%. Meanwhile, after the catalyst is repeatedly used for 5 times, the yield of the biodiesel is still not lower than 80.0 percent.
Furthermore, after the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material repeatedly used for many times is roasted and regenerated, the structure, the texture, the surface acidity and the catalytic performance of the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material are not obviously changed.
Drawings
FIG. 1 is a TEM photograph of an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared in example 1.
FIG. 2 is an XRD spectrum of an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared in example 1.
FIG. 3 is an elemental mapping chart of an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared in example 1.
FIG. 4 is a diagram of example 1 for preparing an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material 2 Adsorption-desorption isotherms (A) and corresponding pore size distribution curves (B).
FIG. 5 is a process of example 1 for preparing ordered mesoporous sulfuric acidNH of zirconium oxide-aluminum composite oxide solid acid material 3 TPD desorption profile.
FIG. 6 is a pyridine-infrared spectrum of an ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared in example 1.
FIG. 7 is a graph showing the effect of the number of repeated use of the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material prepared in example 1 on the yield of biodiesel.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and perform the operations according to the conventional conditions or conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
Example 1.
0.25g of deionized water, 0.32g of citric acid, 3.5g of EO were mixed at 30 ℃ with vigorous stirring 106 PO 70 EO 106 1.65g of aluminum isopropoxide and 1.44g of zirconium oxychloride are sequentially added into 25mL of absolute ethanol, and stirred for 5 hours to be completely dissolved, so as to obtain a clear solution.
And pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating the solution to 80 ℃ for solvothermal pretreatment for 12 hours.
The solution obtained by the thermal pretreatment of the solvent is placed in an open state, volatilization treatment is firstly carried out for 12h at 60 ℃, and thermal polymerization treatment is carried out for 24h after the temperature is increased to 120 ℃.
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 1mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 10, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
As can be seen from the TEM photograph of the sample in fig. 1, the sample has regular and ordered in-line (fig. 1A) and honeycomb (fig. 1B) ordered mesoporous channel structures and highly uniform mesoporous pore diameters, indicating that the sample has an ordered two-dimensional hexagonal mesoporous channel structure.
As can be seen from the small angle XRD spectrum of fig. 2 (fig. 2A), the sample showed a strong diffraction peak and a relatively weak diffraction peak at 2 θ =1.05 and 1.85 °. According to the TEM characterization results (as shown in FIG. 1), the two diffraction peaks can be respectively assigned to the (100) crystal plane diffraction peak and the overlap of the (110) and (200) crystal plane diffraction peaks, indicating that the sample has the diffraction peaks corresponding to the (100) crystal plane diffraction peaks and the (200) crystal plane diffraction peaksp6mmThe long-range ordered two-dimensional hexagonal mesoporous pore structure of the space group. In addition, in the large-angle XRD spectrogram of FIG. 2B, no obvious crystal phase diffraction peak of zirconia or alumina is detected in the sample with the 2 theta of 10-80 degrees, which indicates that Zr and Al species in the mesoporous pore wall of the sample are highly uniformly dispersed.
The elemental mapping analysis results (fig. 3) further demonstrate that Zr, Al and S species can achieve a highly uniform dispersion at the atomic level throughout the sample. By calculation, the Al/Zr atomic ratio in the sample was 1.01, and the S/Zr atomic ratio was 0.22.
From N of FIG. 4 2 As can be seen from the adsorption-desorption isotherm (a) and the corresponding pore size distribution curve (B), the sample exhibits a typical IV-type adsorption isotherm and H1-type hysteresis loop of columnar pores, and shows a very steep capillary coagulation curve (as shown in fig. 4A) within a relative pressure range of 0.6 to 0.8, indicating that the sample has a large and uniformly distributed mesoporous pore size (as shown in fig. 4B). Calculating to obtain the specific surface of the sampleThe volume and pore volume are respectively 320m 2 G and 0.66cm 3 The mesoporous aperture is 8.64 nm.
From sample NH 3 The TPD spectrum (fig. 5) shows that the sample shows four distinct ammonia desorption peaks at 230, 310, 400 and 580 ℃, corresponding to the desorption of the chemisorbed ammonia molecules at the weak, medium, strong and super acid centers of the sample surface. Through calculation of the peak areas of desorption peaks, the total acid amount of the sample is 2.56mmol/g, wherein the acid amounts of the weak acid, the medium acid, the strong acid and the super acid on the surface are respectively 0.75 mmol/g, 0.73 mmol/g, 0.89 mmol/g and 0.19 mmol/g.
From the pyridine adsorption-desorption infrared spectrum (FIG. 6) of the sample, it can be seen that the samples were 1543, 1490 and 1454cm when pyridine was desorbed at 150, 250 and 350 deg.C -1 Three distinct absorption peaks are shown, indicating that both the B acid and the L acid centers are present on the surface of the sample. By desorbing 1543 and 1454cm in the infrared curve with pyridine at different temperatures -1 The acid amount ratio of the total B acid center and the total L acid center of the sample was found to be 1.12 by calculation from the adsorption peak area, wherein the acid amount ratio of the B acid to the L acid was 0.85 and 1.01 in the strong acid center and the medium strong acid center, respectively.
The prepared sample is used as a solid acid catalyst for preparing biodiesel through transesterification of soybean oil and methanol, and the catalytic performance of the catalyst is examined.
According to the molar ratio of soybean oil to methanol of 1: 20, 40g of reactants and 1.2g of catalyst are put into a closed reaction kettle with a stirrer, and the reaction is started at 100 ℃ under the condition of stirring speed of 600rpm for 5 hours.
After the reaction, solid-liquid separation was carried out by a centrifuge. The liquid reaction mixture was first distilled under reduced pressure to remove unreacted methanol, then left to stand until the mixed solution was layered up and down, and a quantitative upper layer solution was taken, diluted with pyridine, and subjected to product composition analysis on a gas chromatograph equipped with a hydrogen Flame Ionization Detector (FID).
The separated solid acid catalyst was washed with methanol and hexane, dried, and then put into use again to examine the catalytic stability of the catalyst.
The catalytic evaluation result (figure 7) shows that the catalytic material can realize the complete conversion of the soybean oil after the reaction is carried out at the low temperature of 100 ℃ for 5 hours, and the yield of the biodiesel in the product can reach 99.8 percent, which indicates that the catalyst has excellent transesterification reaction activity of the biodiesel synthesized from the soybean oil and methanol.
In addition, after 5 times of repeated use, the catalyst can still realize the conversion of 82.9 percent of soybean oil into biodiesel (the yield of the biodiesel is 82.2 percent).
More importantly, after the catalyst is repeatedly used for 5 times and is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the catalyst are not obviously changed compared with those of a fresh catalyst, the complete conversion of soybean oil at the low temperature of 100 ℃ can be realized again, and the yield of the biodiesel reaches 99.6%.
Therefore, the catalyst shows excellent catalytic activity, stability and regeneration performance in the process of biodiesel transesterification reaction synthesized from soybean oil and methanol.
Example 2.
0.35g of deionized water, 1.6g of concentrated hydrochloric acid (36.5wt.%), 0.50g of glacial acetic acid, 3.0g of EO were mixed with vigorous stirring at 35 deg.C 30 PO 70 EO 30 1.325g of aluminum tert-butoxide and 3.49g of zirconium isopropoxide were added to 35mL of anhydrous ethanol in this order, and the mixture was stirred for 2 hours to completely dissolve the aluminum tert-butoxide and the zirconium isopropoxide to obtain a clear solution.
Pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating to 100 ℃ for solvothermal pretreatment for 6 hours.
The solution obtained by the thermal pretreatment of the solvent is placed in an open state, volatilization treatment is firstly carried out for 12h at 70 ℃, and thermal polymerization treatment is carried out for 24h after the temperature is increased to 100 ℃.
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 0.5mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 5, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM, EDX and N 2 The adsorption-desorption and other characteristic results prove that the prepared sample has an ordered two-dimensional hexagonal mesoporous pore structure, the Al/Zr atomic ratio in the sample is 0.49, and Zr, Al and S species can reach atomic level uniform dispersion in the whole sample range. The specific surface area and pore volume of the sample were 308m, respectively 2 G and 0.57cm 3 The mesoporous diameter is 6.81 nm.
NH 3 TPD and pyridine adsorption-desorption infrared characterization results prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.62, 0.81, 0.78 and 0.26mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.68, wherein the acid amount ratio of the B acid to the L acid in the strong acid center to the strong acid center was 1.05 and 1.10, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst.
In the previous 2 times of repeated use processes, the sample can realize the complete conversion of soybean oil, and the yield of the biodiesel is kept above 99.7 percent. Although the conversion rate of soybean oil of the sample is gradually reduced from the 3 rd repeated use, the yield of the biodiesel is kept above 81.2 percent in the 5 repeated use processes.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, 100 percent of complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.7 percent.
Example 3.
0.53g of deionized water, 1.0g of concentrated nitric acid (65wt.%), 0.60g of tartaric acid, 3.5g of EO were mixed with vigorous stirring at 30 deg.C 34 BO 11 EO 34 1.97g of aluminum iso-butoxide and 3.43g of zirconium nitrate are added to 50mL of absolute ethanol in sequence, and stirred for 2 hours to be completely dissolved, so as to obtain a clear solution.
Pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating the solution to 80 ℃ for solvothermal pretreatment for 8 hours.
The solution obtained by the thermal pretreatment of the solvent is placed in an open state, the solvent volatilization treatment is firstly carried out at 80 ℃ for 12h, and the thermal polymerization treatment is carried out for 24h after the temperature is increased to 100 ℃.
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 1.5mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 20, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM, EDX and N 2 The adsorption-desorption and other characteristic results prove that the prepared sample has an ordered two-dimensional hexagonal mesoporous pore structure, the Al/Zr atomic ratio in the sample is 0.98, and Zr, Al and S species can reach atomic level uniform dispersion in the whole sample range. The specific surface area and the pore volume of the sample were 368m, respectively 2 G and 0.42cm 3 The mesoporous aperture is 5.63 nm.
NH 3 The results of TPD and pyridine adsorption-desorption infrared characterization prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.82, 0.94, 0.89 and 0.21mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.10, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.88 and 0.98, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst.
When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the biodiesel reaches more than 99.8 percent. Although the conversion rate of the sample to soybean oil gradually decreases from the 2 nd reuse, the yield of the biodiesel is kept above 81.8% in the 5 times of reuse.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, 100 percent of complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.5 percent.
Example 4.
0.68g of deionized water, 0.25g of oxalic acid, and 3.8g of EO were mixed at 32 ℃ with vigorous stirring 30 PO 70 EO 30 2.18g of aluminum iso-butoxide and 2.0g of zirconium oxychloride are sequentially added into 65mL of absolute ethanol and stirred for 3 hours to be completely dissolved, so as to obtain a clear solution.
And pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating the solution to 60 ℃ for solvothermal pretreatment for 12 hours.
The solution obtained by the thermal pretreatment of the solvent is placed in an open state, the solvent volatilization treatment is firstly carried out at 60 ℃ for 12h, and the thermal polymerization treatment is carried out for 24h after the temperature is increased to 120 ℃.
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 1.0mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 10, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM, EDX and N 2 The adsorption-desorption and other characteristic results prove that the prepared sample has an ordered two-dimensional hexagonal mesoporous pore structure, the Al/Zr atomic ratio in the sample is 2.03, and Zr, Al and S species can reach atomic level uniform dispersion in the whole sample range. The specific surface area and the pore volume of the sample were 381m, respectively 2 G and 0.58cm 3 The mesoporous aperture is 6.17 nm.
NH 3 The infrared characterization results of TPD and pyridine adsorption-desorption prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 1.87, 1.63, 0.82 and 0.11mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.66, wherein the acid amount ratio of the B acid to the L acid in the strong acid center to the strong acid center was 1.25 and 1.31, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst.
In the previous 2 times of repeated use processes, the sample can realize the complete conversion of soybean oil, and the yield of the biodiesel is kept above 99.5 percent. Although the conversion rate of the sample to soybean oil gradually decreases from the 3 rd reuse, the yield of the biodiesel is kept above 80.2% in the 5 times of reuse.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, 100 percent of complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.3 percent.
Example 5.
0.52g of deionized water, 1.5g of citric acid, 4.0g of EO were mixed at 30 ℃ with vigorous stirring 106 PO 70 EO 106 2.12g of aluminum isopropoxide and 2.40g of zirconium isopropoxide are sequentially added to 35mL of absolute ethanol, and stirred for 5 hours to obtain a clear solution.
Pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating the solution to 100 ℃ for solvothermal pretreatment for 6 hours.
Placing the solution obtained by solvent thermal pretreatment in open state, volatilizing the solvent at 70 deg.C for 12 hr, heating to 120 deg.C, and performing thermal polymerization for 24 hr
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 2.5mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 10, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM, EDX and N 2 The adsorption-desorption and other characteristic results prove that the prepared sample has an ordered two-dimensional hexagonal mesoporous pore structure, the Al/Zr atomic ratio in the sample is 1.51, and ZrThe Al and S species can be uniformly dispersed at the atomic level throughout the sample. The specific surface area and the pore volume of the sample were 321m, respectively 2 G and 0.68cm 3 The mesoporous aperture is 9.25 nm.
NH 3 TPD and pyridine adsorption-desorption infrared characterization results prove that weak acid, medium strong acid, strong acid and super strong acid centers exist on the surface of the sample at the same time, and the contents of the centers are 0.82 mmol/g, 1.02 mmol/g, 0.73 mmol/g and 0.20mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.51, wherein the acid amount ratio of the B acid to the L acid in the strong acid center to the strong acid center was 1.35 and 1.21, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst.
In the previous 2 times of repeated use processes, the sample can realize the complete conversion of soybean oil, and the yield of the biodiesel is kept above 99.8 percent. Although the conversion rate of the sample to the soybean oil gradually decreases from the 3 rd reuse, the yield of the biodiesel is kept above 80.6% in the 5 times of reuse.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, 100 percent of complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.4 percent.
Example 6.
1.0g of deionized water, 0.56g of citric acid, 4.9g of EO were mixed at 20 ℃ with vigorous stirring 30 PS, 2.46g of aluminum isopropoxide and 1.5g of zirconium oxychloride are sequentially added into 35mL of absolute ethanol and stirred for 5h to obtain a clear solution.
And pouring the obtained clear solution into a sealed high-pressure reaction kettle, and heating the solution to 70 ℃ for solvothermal pretreatment for 10 hours.
The solution obtained by the thermal pretreatment of the solvent is placed in an open state, the solvent volatilization treatment is firstly carried out at 60 ℃ for 12h, and the thermal polymerization treatment is carried out for 24h after the temperature is increased to 120 ℃.
And (3) heating the obtained solid to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 5h, removing the organic template agent existing in the mesoporous pore channel, and preparing the ordered mesoporous zirconium-aluminum composite oxide.
And (2) placing the obtained ordered mesoporous zirconium-aluminum composite oxide into a 1.8mol/L sulfuric acid solution according to the solid/liquid volume ratio of 1: 20, stirring for 30min at 30 ℃, performing suction filtration, drying for 12h at 100 ℃, and roasting for 5h at 550 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM, EDX and N 2 The adsorption-desorption and other characteristic results prove that the prepared sample has an ordered two-dimensional hexagonal mesoporous pore structure, the Al/Zr atomic ratio in the sample is 1.41, and Zr, Al and S species can reach atomic level uniform dispersion in the whole sample range. The specific surface area and pore volume of the sample were 346m, respectively 2 G and 0.58cm 3 The mesoporous aperture is 7.01 nm.
NH 3 The infrared characterization results of TPD and pyridine adsorption-desorption prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.88, 0.92, 0.81 and 0.23mmol/g respectively. The acid amount ratio of the total B acid center and the L acid center on the surface of the sample was 1.22, wherein the acid amount ratio of the B acid to the L acid in the strong acid center and the strong acid center was 1.00 and 1.03, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst.
When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the biodiesel reaches 99.8%. Although the conversion rate of the sample to the soybean oil gradually decreases from the 2 nd reuse, the yield of the biodiesel is kept above 80.7% in the 5 times of reuse.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, 100 percent of complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.5 percent.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (8)
1. An ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material is used as a catalyst for transesterification of soybean oil and methanol to synthesize biodiesel, and has a regular and ordered two-dimensional hexagonal mesoporous pore structure with a specific surface area of 150-420 m 2 Per gram, pore volume 0.3-1.2 cm 3 The pore diameter is 4.0-18.0 nm, the molar ratio of zirconium atoms to aluminum atoms in the pore walls can be adjusted within the range of 0.1-10, and the acid amount, the acid density, the ratio of B acid centers to L acid centers and the content of super acid centers on the surface of the pore walls are respectively 0.1-5.2 mmol/g and 0.0001-0.018 mmol/m 2 0.01-2.1 and 0-0.8 mmol/g, and is prepared according to the following steps:
1) dissolving inorganic acid, organic carboxylic acid and a block copolymer nonionic surfactant in a mixed solution of deionized water and absolute ethyl alcohol according to a molar mixture ratio of zirconium source, aluminum source, organic carboxylic acid, inorganic acid, deionized water, absolute ethyl alcohol and block copolymer nonionic surfactant of = (10-100): (0-40): (10-120): (50-300): 1000-3000): 1, slowly adding the zirconium source and the aluminum source, and stirring to obtain a clear solution;
2) placing the clear solution in a sealed high-pressure reaction kettle, and carrying out solvent thermal pretreatment for 5-24 hours at the temperature of 60-120 ℃ to obtain a surfactant composite micelle solution wrapping zirconium and aluminum hydroxyl species;
3) volatilizing the surfactant composite micelle solution to be dry, heating to 100-180 ℃, and carrying out thermal polymerization treatment for 24-48 h to obtain an ordered mesoporous zirconium-aluminum composite oxide wrapping the surfactant micelle;
4) roasting in the air to remove the surfactant micelle existing on the ordered mesoporous zirconium-aluminum composite oxide wrapping the surfactant micelle to obtain the ordered mesoporous zirconium-aluminum composite oxide;
5) and placing the ordered mesoporous zirconium-aluminum composite oxide in a sulfuric acid solution for dipping treatment, and then roasting at 300-650 ℃ to prepare the ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material.
2. The solid acid material according to claim 1, wherein the block copolymer type nonionic surfactant is a nonionic block copolymer having a structural formula of EOnPOmEOn, EOnBOmEOn or EOnPS, wherein polyethylene oxide is a hydrophilic block, polypropylene oxide, polybutylene oxide or polystyrene is a hydrophobic block, n = 10-200, and m = 5-120; wherein EO represents ethylene oxide, PO represents propylene oxide, BO represents butylene oxide, and PS represents polystyrene.
3. The solid acid material as claimed in claim 1, wherein the zirconium source is one of zirconium oxychloride, zirconium isopropoxide, zirconium acetate or zirconium nitrate, or a mixture of any proportion of the above.
4. The solid acid material as claimed in claim 1, wherein the aluminum source is one of aluminum isopropoxide, aluminum tert-butoxide, aluminum iso-butoxide, aluminum nitrate or aluminum chloride, or a mixture of the above in any proportion.
5. The solid acid material according to claim 1, wherein the inorganic acid is hydrochloric acid, nitric acid or phosphoric acid.
6. The solid acid material according to claim 1, characterized in that the organic carboxylic acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
7. The solid acid material according to claim 1, wherein the ordered mesoporous zirconium-aluminum composite oxide encapsulating the surfactant micelle is calcined in air at 400 to 750 ℃ for 3 to 5 hours.
8. The solid acid material according to claim 1, wherein the ordered mesoporous zirconium-aluminum composite oxide is impregnated in a sulfuric acid solution having a concentration of 0.1 to 2mol/L at a solid/liquid volume ratio of (0.05 to 1): 1.
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