CN117899926A - Bimetal supported Ti-SBA-15 catalyst and preparation method and application thereof - Google Patents
Bimetal supported Ti-SBA-15 catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910002520 CoCu Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000012691 Cu precursor Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 64
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-M 3-carboxy-2,3-dihydroxypropanoate Chemical compound OC(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-M 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 12
- 235000002906 tartaric acid Nutrition 0.000 abstract description 12
- 239000011975 tartaric acid Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 16
- 238000011068 loading method Methods 0.000 description 11
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003225 biodiesel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a bimetal supported Ti-SBA-15 catalyst and a preparation method and application thereof, belonging to the technical field of catalyst preparation. The bimetallic in the catalyst is CoCu, the load of the CoCu accounts for 5-25wt% of the catalyst, and the mass ratio of Co to Cu is 0.25-4:1; the catalyst can be successfully prepared by a one-step hydrothermal synthesis-isovolumetric impregnation composite method, and a cobalt precursor and a copper precursor are impregnated and dispersed on a Ti-SBA-15 carrier to obtain the catalyst; the catalyst can be applied to the reaction of preparing the tartaric acid by catalyzing the selective oxidation of the glycerol, wherein oxides of two metals in the catalyst have a synergistic effect on the catalysis of the oxidation reaction, and compared with single metal, the catalyst has higher selectivity on the target product of the tartaric acid, thereby realizing the high-efficiency conversion of the glycerol (the conversion rate is more than 60%) and the high selectivity of the tartaric acid (the selectivity is more than 50%).
Description
Technical Field
The invention relates to a preparation method and application of a catalyst, in particular to a bimetallic supported Ti-SBA-15 catalyst and a preparation method and application thereof.
Background
Along with exhaustion of fossil energy sources such as coal, petroleum, natural gas and the like and deterioration of ecological environment, development of renewable resources and energy sources is urgently needed in modern society, and economic, energy-saving and environment-friendly technological processes are developed based on the renewable resources and energy sources to realize sustainable production of fuels and fine chemicals. Compared with fossil fuel, biodiesel is taken as a renewable liquid fuel, has the advantages of high cetane number, low pollution, easy degradation, good combustion performance and the like, is considered as a promising traditional fossil fuel substitute, and is widely developed and utilized. When biodiesel is produced on a large scale by transesterification, the yield of the byproduct crude glycerol is excessive, the supply and the demand are over, the price is suddenly reduced, the further popularization of the biodiesel is restricted, and therefore, the conversion of glycerol into chemicals with high added value is one of the keys for the popularization of the biodiesel.
Glycerol is a highly functionalized molecule having three hydroxyl groups that can be used to derive a number of high value-added chemical intermediates by oxidation, hydrogenolysis, dehydration, esterification, oxidative carbonylation, transesterification, and polymerization. Wherein, the chemical with high equivalent lattice of tartaric acid, dihydroxyacetone, glyceric acid and glyceraldehyde can be obtained by the selective oxidation of glycerin. The tartaric acid has wide application in the field of medicines, can inhibit the conversion of saccharides into fat in a human body, prevent fat accumulation in the body, has the effects of losing weight and preventing coronary heart disease, and can be used as a medicament for treating obesity; can also be used for synthesizing cleaning agents, chelating agents and the like.
The catalysts used for the selective oxidation of glycerol at present mostly use noble metals as active components. The metals widely used in the noble metal catalysts are Pt, au and Ag, however, the catalytic active sites of the noble metal catalysts are easily poisoned by reaction intermediates, the catalytic activity is greatly influenced by the size, the storage amount is small, the cost is high, and the industrialization is difficult to realize. Based on this, how to prepare a catalyst with low cost and high efficiency and stability is a problem to be solved.
Disclosure of Invention
The invention aims to: the key purpose of the invention is to provide a preparation method and application of a non-noble metal CoCu supported Ti-SBA-15 catalyst, and the method is simple to operate, mild in condition and low in production cost, and is expected to realize industrial production. The invention aims to provide a bimetal supported Ti-SBA-15 catalyst which is low in cost, efficient and stable; the invention also aims to provide a preparation method of the bimetallic supported Ti-SBA-15 catalyst; the invention also aims to provide an application of the bimetallic supported Ti-SBA-15 catalyst in preparing the tartaric acid by catalyzing the selective oxidation of the glycerol.
The technical scheme is as follows: the bimetallic supported Ti-SBA-15 catalyst is CoCu, the load of the CoCu accounts for 5-25wt% of the catalyst, and the mass ratio of Co to Cu is 0.25-4:1.
The preparation method of the bimetallic supported Ti-SBA-15 catalyst comprises the following steps: and (3) soaking the cobalt and copper precursors and the Ti-SBA-15 carrier at room temperature (an equal volume soaking compounding method) to obtain a mixed solution, drying and calcining to obtain the bimetal supported Ti-SBA-15 catalyst.
Preferably, the cobalt precursor is cobalt nitrate or cobalt chloride; the copper precursor is copper nitrate, copper sulfate or copper chloride.
Preferably, the calcination temperature is 500-550 ℃, the calcination time is 2-4 h, the heating rate is 1-5 ℃/min, and the impregnation time is 12-48 h.
Preferably, the preparation method of the Ti-SBA-15 carrier comprises the following steps: (1) Dissolving a surfactant polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in a hydrochloric acid solution, and stirring and dissolving to form a solution A; (2) Dropwise adding a silicon source, a titanium source and acetylacetone into the solution A, stirring to form a solution B, transferring the solution B into a reaction kettle, ageing at 80-150 ℃ to obtain a white solid, and roasting at 500-550 ℃ after suction filtration, washing and drying to obtain the Ti-SBA-15 carrier.
Preferably, the concentration of the hydrochloric acid solution in the step (1) is 1-2 mol/L; the mass volume ratio of the surfactant to the hydrochloric acid is 3-6 g/100-250 mL.
Preferably, in the step (2), the silicon source is ethyl orthosilicate, the titanium source is tetrabutyl titanate, the silicon-titanium molar ratio of the silicon source ethyl orthosilicate to the titanium source tetrabutyl titanate is 10-100:1, and the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.4-1.2.
Preferably, the solution A is stirred for 2 to 12 hours, and the stirring temperature is 30 to 50 ℃; stirring the solution B for 24-72 h at 30-50 ℃; the aging time is 12-48 h, and the roasting time is 6-8 h.
The bimetallic supported Ti-SBA-15 catalyst can be applied to the preparation of the tartaric acid by catalyzing the selective oxidation of glycerol.
Specific operations for catalyzing the reaction of selective oxidation of glycerol to produce tartaric acid include: 0.5-0.6 g of glycerol is dissolved in 20-30 mL of deionized water, 0.8-0.9 g of sodium hydroxide is dissolved in 10-20 mL of deionized water, the solution and 0.1-0.5 g of catalyst are transferred into a three-necked flask, 0.6-3 mL of 30% hydrogen peroxide is dropwise added, stirring reaction is carried out for 2-12 h at 40-100 ℃, and the catalyst is separated by filtration.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The CoCu supported Ti-SBA-15 catalyst takes a Ti-modified SBA-15 molecular sieve with ordered mesoporous pore canal as a carrier, and regulates and controls the adsorption and diffusion of reactants and products by utilizing the pore canal limiting effect of the SBA-15 molecular sieve, thereby improving the high-efficiency selectivity of target products; then Ti is introduced to modify the molecular sieve based on the limit characteristic of the molecular sieve SBA-15 pore canal, the metal active components are anchored and regulated by the introduction of Ti, the glycerol is favorably converted into the tartaric acid, and the selectivity of the tartaric acid is further improved; the introduction of the Co and Cu bimetallic materials not only reduces the production cost of the reaction, but also has a synergistic effect on the catalysis of the oxidation reaction by the oxides of the two metals in the catalytic oxidation reaction, and compared with single metal, the selectivity of the oxide to the target product of the bitartrate is higher, so that the high-efficiency conversion (the conversion rate is more than 60%) of the glycerol and the high selectivity (the selectivity is more than 50%) of the bitartrate are realized; (2) Simple preparation process, low cost and mild reaction condition.
Drawings
FIG. 1 is an XRD pattern of CoCu/Ti-SBA-15 prepared in example 1;
FIG. 2 is a FT-IR chart of CoCu/Ti-SBA-15 prepared in example 1;
FIG. 3 is an SEM image of CoCu/Ti-SBA-15 prepared in example 1;
FIG. 4 is a graph of the performance of the CoCu bimetallic supported Ti-SBA-15 catalyst of application example 1 versus the Cu supported Ti-SBA-15 catalyst of comparative example 1 (including glycerol conversion and selectivity to tartaric acid).
Detailed Description
The technical scheme of the invention is further described below with reference to the embodiment and the attached drawings.
Example 1
(1) 6.0G of a surfactant polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, abbreviated as P123, was dissolved in 225mL of a 2mol/L hydrochloric acid solution and stirred at 40℃for 4 hours until dissolved to form a solution A.
(2) Slowly dripping silicon source tetraethoxysilane, titanium source tetrabutyl titanate (the molar ratio of Si in the tetraethoxysilane to Ti in the tetrabutyl titanate is 20) and acetylacetone into the solution A (the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.6), continuously stirring at 40 ℃ for 24 hours to form a solution B, transferring the solution B into a hydrothermal reaction kettle, aging at 100 ℃ for 24 hours to obtain white solid, filtering, washing for three times, drying to obtain white powder, and calcining at 550 ℃ for 6 hours (the heating rate is 5 ℃/min) to obtain the Ti-SBA-15 carrier.
(3) 0.074G of Co (NO 3)2 and 0.057g of Cu (NO 3)2 water solution (total water mass: 1.8 g)) are added dropwise to 0.3g of Ti-SBA-15 carrier under the action of ultrasound, then stirred for 24 hours at room temperature to obtain a C solution, the C solution is dried in a 100 ℃ oven, and the C solution is heated to 550 ℃ in a muffle furnace and calcined for 4 hours (the heating rate is 5 ℃/min) to prepare the bimetallic CoCu-loaded Ti-SBA-15 catalyst, wherein the Co loading amount is 5wt%, and the Cu loading amount is 5wt%, so that the catalyst is called Co 1Cu1/Ti-SBA-15.
FIG. 1 is an XRD pattern of Co 1Cu1/Ti-SBA-15 catalyst of this example, from which it is seen that Co exists as tricobalt tetraoxide and Cu exists as copper oxide. FIG. 2 is a FT-IR chart of Co 1Cu1/Ti-SBA-15 catalyst in this example, from which it is seen that the absorption peak occurring at 960cm -1 is attributed to stretching vibration of the Ti-O-Si bond, demonstrating successful synthesis of Ti-SBA-15. FIG. 3 is an SEM image of a Co 1Cu1/Ti-SBA-15 catalyst of this example, from which it is seen that the catalyst has a short rod morphology and that the rods are clustered together in bundles, which is typical of the SBA-15 morphology.
Comparative example
0.114G of Cu (NO 3)2 aqueous solution (total water mass is 1.8 g) is added into 0.3g of Ti-SBA-15 carrier dropwise under the action of ultrasound, then stirred for 24 hours at room temperature, then dried in a 100 ℃ oven, and finally heated to 550 ℃ in a muffle furnace and calcined for 4 hours (heating rate is 5 ℃/min) to prepare the single-metal Cu-supported Ti-SBA-15 catalyst, wherein the Cu load is 10wt%, and the single-metal Cu-supported Ti-SBA-15 catalyst is recorded as Cu/Ti-SBA-15.
Example 2
(1) 6.0G of surfactant P123 are dissolved in 225mL of 2mol/L hydrochloric acid solution and stirred at 40℃for 4h until dissolved to form A solution.
(2) Slowly dripping silicon source tetraethoxysilane, titanium source tetrabutyl titanate (the molar ratio of Si in the tetraethoxysilane to Ti in the tetrabutyl titanate is 20) and acetylacetone into the solution A (the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.6), continuously stirring at 40 ℃ for 24 hours to form a solution B, transferring the solution B into a hydrothermal reaction kettle, aging at 100 ℃ for 24 hours to obtain white solid, filtering, washing for three times, drying to obtain white powder, and calcining at 550 ℃ for 6 hours (the heating rate is 5 ℃/min) to obtain the Ti-SBA-15 carrier.
(3) 0.074G of Co (NO 3)2 and 0.114g of Cu (NO 3)2 water solution (total water mass is 1.8 g)) are dripped into 0.3g of Ti-SBA-15 carrier under the action of ultrasound, then stirred for 24 hours at room temperature to obtain a C solution, the C solution is dried in a 100 ℃ oven, and the C solution is heated to 550 ℃ in a muffle furnace and calcined for 4 hours (the heating rate is 5 ℃/min) to prepare the bimetallic CoCu-loaded Ti-SBA-15 catalyst, wherein the Co loading amount is 5wt% and the Cu loading amount is 10wt%.
Example 3
(1) 6.0G of surfactant P123 are dissolved in 225mL of 2mol/L hydrochloric acid solution and stirred at 40℃for 4h until dissolved to form A solution.
(2) Slowly dripping silicon source tetraethoxysilane, titanium source tetrabutyl titanate (the molar ratio of Si in the tetraethoxysilane to Ti in the tetrabutyl titanate is 20) and acetylacetone into the solution A (the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.6), continuously stirring at 40 ℃ for 24 hours to form a solution B, transferring the solution B into a hydrothermal reaction kettle, aging at 100 ℃ for 24 hours to obtain white solid, filtering, washing for three times, drying to obtain white powder, and calcining at 550 ℃ for 6 hours (the heating rate is 5 ℃/min) to obtain the Ti-SBA-15 carrier.
(3) 0.074G of Co (NO 3)2 and 0.228g of Cu (NO 3)2 water solution (total water mass is 1.8 g)) are dripped into 0.3g of Ti-SBA-15 carrier under the action of ultrasound, then stirred for 24 hours at room temperature to obtain a C solution, the C solution is dried in a 100 ℃ oven, and the C solution is heated to 550 ℃ in a muffle furnace and calcined for 4 hours (the heating rate is 5 ℃/min) to prepare the bimetallic CoCu-loaded Ti-SBA-15 catalyst, wherein the Co loading amount is 5wt% and the Cu loading amount is 20wt%.
Example 4
(1) 6.0G of surfactant P123 are dissolved in 225mL of 2mol/L hydrochloric acid solution and stirred at 40℃for 4h until dissolved to form A solution.
(2) Slowly dripping silicon source tetraethoxysilane, titanium source tetrabutyl titanate (the molar ratio of Si in the tetraethoxysilane to Ti in the tetrabutyl titanate is 20) and acetylacetone into the solution A (the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.6), continuously stirring at 40 ℃ for 24 hours to form a solution B, transferring the solution B into a hydrothermal reaction kettle, aging at 100 ℃ for 24 hours to obtain white solid, filtering, washing for three times, drying to obtain white powder, and calcining at 550 ℃ for 6 hours (the heating rate is 5 ℃/min) to obtain the Ti-SBA-15 carrier.
(3) 0.148G of Co (NO 3)2 and 0.057g of Cu (NO 3)2 water solution (total water mass is 1.8 g)) are dripped into 0.3g of Ti-SBA-15 carrier under the action of ultrasound, then stirred for 24 hours at room temperature to obtain a C solution, the C solution is dried in a 100 ℃ oven, and the C solution is heated to 550 ℃ in a muffle furnace and calcined for 4 hours (the heating rate is 5 ℃/min) to prepare the bimetallic CoCu-loaded Ti-SBA-15 catalyst, wherein the Co loading amount is 10wt% and the Cu loading amount is 5wt%.
Example 5
(1) 6.0G of surfactant P123 are dissolved in 225mL of 2mol/L hydrochloric acid solution and stirred at 40℃for 4h until dissolved to form A solution.
(2) Slowly dripping silicon source tetraethoxysilane, titanium source tetrabutyl titanate (the molar ratio of Si in the tetraethoxysilane to Ti in the tetrabutyl titanate is 20) and acetylacetone into the solution A (the molar ratio of the tetrabutyl titanate to the acetylacetone is 1:0.6), continuously stirring at 40 ℃ for 24 hours to form a solution B, transferring the solution B into a hydrothermal reaction kettle, aging at 100 ℃ for 24 hours to obtain white solid, filtering, washing for three times, drying to obtain white powder, and calcining at 550 ℃ for 6 hours (the heating rate is 5 ℃/min) to obtain the Ti-SBA-15 carrier.
(3) 0.296G of Co (NO 3)2 and 0.057g of Cu (NO 3)2 water solution (total water mass is 1.8 g)) are dripped into 0.3g of Ti-SBA-15 carrier under the action of ultrasound, then stirred for 24 hours at room temperature to obtain a C solution, the C solution is dried in a 100 ℃ oven, and the C solution is heated to 550 ℃ in a muffle furnace and calcined for 4 hours (the heating rate is 5 ℃/min) to prepare the bimetallic CoCu-loaded Ti-SBA-15 catalyst, wherein the Co loading amount is 20wt% and the Cu loading amount is 5wt%.
Application example
0.553G of glycerin was dissolved in 20mL of deionized water, 0.8g of sodium hydroxide was dissolved in 10mL of deionized water, and Co 1Cu1/Ti-SBA-15 catalyst prepared in example 1 and Cu/Ti-SBA-15 prepared in comparative example 1 were added to the above solutions, respectively, 30% hydrogen peroxide was added dropwise in 1.23mL, and the reaction was stirred at 80℃for 4 hours, and the catalyst was isolated by filtration.
The test shows that the conversion rate of the catalyst Co 1Cu1/Ti-SBA-15 to glycerol in the reaction of preparing the tartaric acid by selectively oxidizing the glycerol is 63.8%, and the selectivity is 54.5%.
FIG. 4 is a graph showing the comparison of the catalytic performance of the CoCu bimetallic supported Ti-SBA-15 catalyst with the same metal loading in the application example and the Cu supported Ti-SBA-15 catalyst in the comparative example, and the graph shows that the glycerol conversion rate and the bitartrate selectivity of the bimetallic Co 1Cu1/Ti-SBA-15 catalyst are higher than those of the monometal Cu/Ti-SBA-15 catalyst, so that the catalytic reaction activity can be effectively improved by dispersing the bimetallic CoCu on the Ti-SBA-15, and the selectivity of a target product can be improved.
Claims (10)
1. The bimetallic supported Ti-SBA-15 catalyst is characterized in that the bimetallic is CoCu, the load of the CoCu accounts for 5-25wt% of the catalyst, and the mass ratio of Co to Cu is 0.25-4:1.
2. A method for preparing the bimetallic supported Ti-SBA-15 catalyst of claim 1, comprising the steps of: and (3) soaking cobalt and copper precursors and the Ti-SBA-15 carrier at room temperature to obtain a mixed solution, drying and calcining to obtain the bimetal supported Ti-SBA-15 catalyst.
3. The method for preparing a bimetallic supported Ti-SBA-15 catalyst according to claim 2, wherein the cobalt precursor is cobalt nitrate or cobalt chloride; the copper precursor is copper nitrate, copper sulfate or copper chloride.
4. The method for preparing a bimetallic supported Ti-SBA-15 catalyst according to claim 2, wherein the calcination temperature is 500-550 ℃, the calcination time is 2-4 hours, the heating rate is 1-5 ℃/min, and the impregnation time is 12-48 hours.
5. The method for preparing a bimetallic supported Ti-SBA-15 catalyst according to claim 2, characterized in that the method for preparing a Ti-SBA-15 carrier comprises the steps of: (1) Dissolving a surfactant polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in a hydrochloric acid solution, and stirring and dissolving to form a solution A; (2) Dropwise adding a silicon source, a titanium source and acetylacetone into the solution A, stirring to form a solution B, transferring the solution B into a reaction kettle, ageing at 80-150 ℃ to obtain a white solid, and roasting at 500-550 ℃ after suction filtration, washing and drying to obtain the Ti-SBA-15 carrier.
6. The method for preparing a bimetallic supported Ti-SBA-15 catalyst according to claim 5, wherein the concentration of the hydrochloric acid solution in the step (1) is 1-2 mol/L; the mass volume ratio of the surfactant to the hydrochloric acid is 3-6 g/100-250 mL.
7. The preparation method of the bimetal supported Ti-SBA-15 catalyst according to claim 5, wherein in the step (2), the silicon source is ethyl orthosilicate, the titanium source is tetrabutyl titanate, the silicon-titanium mole ratio of the silicon source ethyl orthosilicate to the titanium source tetrabutyl titanate is 10-100:1, and the mole ratio of the tetrabutyl titanate to the acetylacetone is 1:0.4-1.2.
8. The method for preparing a bimetallic supported Ti-SBA-15 catalyst according to claim 5, wherein the time of stirring the solution A is 2-12 hours and the stirring temperature is 30-50 ℃; stirring the solution B for 24-72 h at 30-50 ℃; the aging time is 12-48 h, and the roasting time is 6-8 h.
9. Use of the bimetallic supported Ti-SBA-15 catalyst of claim 1 in the catalytic selective oxidation of glycerol to produce bitartrate.
10. The use according to claim 9, wherein the application method comprises: dissolving 0.5-0.6 g of glycerol in 20-30 mL of deionized water, dissolving 0.8-0.9 g of sodium hydroxide in 10-20 mL of deionized water, uniformly mixing the solution with 0.1-0.5 g of catalyst, transferring the mixture into a three-necked flask, dropwise adding 0.6-3 mL of 30% hydrogen peroxide, stirring at 40-100 ℃ for reacting for 2-12 h, and filtering to separate the catalyst.
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