CN103977837A - Hierarchical-pore carrier loaded nanogold cyclohexane oxidation catalyst and preparation and application thereof - Google Patents
Hierarchical-pore carrier loaded nanogold cyclohexane oxidation catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a hierarchical-pore carrier loaded nanogold cyclohexane oxidation catalyst and preparation and application thereof. The catalyst is a heteropolyacid (HPA)-nano precious metal supramolecular compound loaded on a hierarchical mesoporous aluminophosphate-silica composite material. The structural formula is Au-HPA/AlPO4-SiO2. The preparation method comprises the following steps: preparing a HPA stable nano precious metal colloidal solution by using chloroauric acid, silver nitrate and palladium chloride acid; mixing pseudo-boehmite, phosphoric acid, water, N-searamidopropyl dmethylamine or N-oil-based propane diamine to form a mixed solution A, and mixing tetraethl silicate, a triblock copolymer P123 and water to form a solution B; mixing the solution A and the solution B to form uniform sol; slowly adding the sol into the HPA stable nano precious metal colloidal solution to form the gel; performing hydrothermal treatment on the gel; washing, drying and calcining the filtered solids, thus obtaining the product. The catalyst is simple and convenient to operate, has high activity, can be easily separated from the product and has good recycling performance.
Description
Technical field
The invention belongs to chemical field, be specifically related to the carrier loaded nm of gold cyclohexane oxidation catalyst of a kind of multi-stage porous and preparation and application.
Background technology
Cyclohexane oxidation can obtain two kinds of important oxidation product cyclohexanol and cyclohexanone, is commonly called as KA oil, is the important intermediate of synthesizing adipic acid and caprolactam, and adipic acid and caprolactam are the raw materials of manufacturing nylon-6 and nylon 66.More than 90% KA oil is to produce by cyclohexane oxidation, and only 4% left and right of the cyclohexane conversion of industrial cyclohexane oxidation, selective 80% left and right of KA oil, therefore, improves by catalyst that to improve cyclohexane oxidation efficiency and KA oil productive rate be the focus of research always.Taking oxygen as oxidant, under solvent-free and additive, carry out the synthetic KA oil of cyclohexane oxidation, process is environmental protection more, meet sustainable development requirement, many reports have been studied cyclohexane dioxygen oxidation catalyst system, comprise rare earth or transition metal-type doped molecular sieve, metalloporphyrin, encircle transient metal complex, noble metal catalyst etc. greatly, the noble metal catalyst that wherein nm of gold is representative shows good catalytic activity and selective, has commercial Application potentiality.
Noble metal catalyst, due to its catalytic activity can not be substituted and selective, in hydrogenating reduction, dehydrogenation oxidation, catalytic reforming, coupling, desulfurization, carbonylation and asymmetric syntheses, is all very important good catalyst.As nm of gold and the nanometer gold alloy catalyst of solvent-free cyclohexane dioxygen oxidation, normally by and carrier coprecipitation (CP) or deposition-precipitation (DP) prepare.Document 1 is with Na
2siO
3, AlCl
3, gold chloride is raw material, taking tetrapropyl base ammonium bromide as template by the then synthetic Au/ZSM-5 (Suo Jishuan etc., Chem.Commun.2004,904-905) of method of high-temperature calcination of co-precipitation Hydrothermal Synthesis.Document 2 becomes liquor argenti nitratis ophthalmicus after collargol with sodium borohydride reduction, join in the synthetic colloidal sol of MCM-41 of cetyl ammonium bromide, tetraethyl orthosilicate, composition, make Ag/MCM-41 (Zhou Jicheng etc. by then high-temperature roasting method of co-precipitation, Catal.Lett.2006,108,49-54).Patent CN102553586 is by containing cerium composition metal oxidation nanometer Au catalyst containing cerium complex metal hydroxide and the preparation of nm of gold coprecipitation method, for not comprising the catalytic hydrogenation of aldehyde.But coprecipitation is prepared the deficiency of load nano particle and is; noble metal nano particles part is dispersed in carrier surface; because the isoelectric point of inorganic carrier is conventionally lower; after template is removed in high-temperature roasting; under unprotect agent action condition, only cannot avoid active nano noble metal to reunite and grow up on carrier by the spatial limitation effect of carrier hole.In order to improve the characteristic that on carrier, nano particle is easily reunited, carrier is carried out to base group modification, by the coordination stabilized nanoscale particle between modification group and nano metal particles, as document 3 adopts deposition-intermediate processing, to be with sulfydryl organosilan and tetraethyl orthosilicate copolymerization condensation to form the carrier loaded nm of gold of sulfydryl modification, modify sulfydryl and nm of gold coordination and play stabilization, do not decompose and come off from carrier but the method for the high temperature that document is taked (500 DEG C) roasting Kaolinite Preparation of Catalyst is difficult to ensure the organic sulfydryl of stabilizing agent.Because the catalytic activity of nano-noble metal catalyst is dispersed closely related with nano noble metal particles size on carrier with nano-noble metal, therefore, be necessary nano-noble metal catalyst preparation method to improve, select suitable stabilizing agent and carrier, control nano-noble metal and on carrier, there is high activity, dispersiveness and stability.
The stabilizing agent of preparing metal nanoparticle mainly contains ionic and nonionic surface active agent, as PVP, citrate, aliphatic hydrocarbon quaternary ammonium salt etc.Similar with ionic organic stabilizer, be with different cationic heteropolyacid salts also metal nanoparticle to be had to stabilization, with the larger heteropolyanion of the volume of many negative electrical charges, with produce stronger electrostatic adsorption with anti-electric charge metal micelle, simultaneously, between multiple end oxygen atoms that heteropolyanion exists and zero-valent metal, also there is coordination, promote the stable of metal nanoparticle, and the heat treatment process structure that the inorganic compound person's character of heteropolyacid salt makes it to tolerate supported catalyst while preparing is not destroyed, be more suitable for as the stabilizing agent of preparing nano-noble-metal-loaded catalyst.Foreign literature 4 has been summed up heteropoly acid and has stablized preparation method (the Yifeng Wang of simple metal and metal oxide nanoparticles, I.A.Winstock, Chem.Soc.Rev., 2012,41,7479-7496), under suitable synthesis condition, nano-particles size is controlled, and the redox active of heteropolyacid salt uniqueness gives heteropolyacid salt stable metal nano-particle compound better redox active simultaneously.Multistage mesoporous material and other permeability material comparisons, have the crosslinked structure of high specific area and multi-stage porous, more can meet diffusion and reaction requirement, and foreign literature 5 has compared mesoporous SBA-15, and KIT-6 and classifying porous HMS are carrier A u/CeO
2/ SiO
2cO oxidation reaction performance, the golden nanometer particle that classifying porous HMS is carrier and CeO
2dispersiveness and diffusivity better, activity the highest (Li Wencui etc., Micropor.Mesopor.Material.2012,158,7-12).It is the advantages that stabilizing agent is prepared metal nanoparticle and multistage mesoporous carrier material that the present invention is intended to heteropolyacid salt, prepares stable reused supported nano-gold and billon catalyst for the reaction of the synthetic KA oil of solvent-free cyclohexane oxidation.
Summary of the invention
One of object of the present invention is to provide a kind of and highly actively prepares golden nanometer particle taking heteropolyacid salt as stabilizing agent, and loads on the nm of gold heterogeneous catalyst on multi-stage porous aluminum phosphate-silica complex carrier.This catalyst is applied to the direct oxidation reaction of solvent-free cyclohexane and molecular oxygen, and reaction equation is as follows:
The carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous of the present invention, it is a kind of heteropoly acid (HPA)-nano-noble metal super molecular compound that is carried on multistage mesoporous aluminum phosphate-silicon dioxide composite material, its structural formula is: Au-HPA/AlPO
4-SiO
2.
Specifically, described heteropoly acid is the one in Keggin type phosphorus molybdenum, phosphorus tungsten, phosphorus molybdenum one vanadium, phosphorus molybdenum two vanadium, phosphorus tungsten one vanadium and phosphorus tungsten two vanadium heteropoly acids.
Described nano-noble-metal-loaded is single nm of gold, nanogold-silver alloy and nm of gold-palldium alloy.
Described nano-noble metal content is 0.3～2.5% of carrier quality, and the particle diameter of nano-noble metal is 1-20nm.
The mesoporous scope of described multistage mesoporous aluminum phosphate-silica complex carrier is 2-7nm, and the mole ratio of aluminum phosphate and silica is 1:1.
Two of object of the present invention is to provide the preparation method of the carrier loaded nm of gold cyclohexane oxidation catalyst of above-mentioned multi-stage porous, and it comprises the step of following order:
(1) taking gold chloride as Jin Yuan, silver nitrate is silver-colored source, the acid of chlorine palladium is for preparing heteropoly acid stabilized nanoscale precious metal colloid solution in palladium source: by the gold chloride of the gold chloride of single gold chloride or 1:1 mixed in molar ratio and silver nitrate or 1:1 mixed in molar ratio and the acid of chlorine palladium, add deionized water and be made into the solution that concentration is 2～5mM, add again solid heteropoly acid, stir lower mixing, wherein, the mol ratio of noble metal and heteropoly acid is 5/1～15/1; After 1 hour, add the NaBH of excessive 0.1M
4solution, adds NaBH
4mole is 3～10 times of noble metal mole in solution, and stirring reaction 3～5 hours under room temperature, makes heteropoly acid stabilized nanoscale precious metal colloid solution;
(2) taking boehmite as aluminium source, by boehmite and phosphoric acid, water, N-stearyl propane diamine or N-oil base propane diamine by 1Al:1P:0.06～0.25N-stearyl propane diamine or N-oil base propane diamine: the mixed in molar ratio of 50 water becomes solution A; Taking tetraethyl orthosilicate as silicon source, tetraethyl orthosilicate, triblock polymer P123, water are pressed to 1Si:0.016P123:50～100H
2the mixed in molar ratio of O, with 1M salt acid for adjusting pH be 3 formation solution B; Solution A and solution B are mixed and stirred and within 2 hours, form even colloidal sol;
(3) step (2) gained colloidal sol is slowly added in step (1) gained heteropoly acid stabilized nanoscale precious metal colloid solution, under room temperature, stir 20～36 hours, dripping mass percent concentration again and be 25% the TBAH aqueous solution, to regulate pH value be 8～9, continue to stir 2～4 hours, form gel;
(4) previous step gained gel is transferred in water heating kettle to hydrothermal treatment consists 48 hours at 120 DEG C, the solid after then filtering, wash by deionized water, dry at 100 DEG C again, calcine 4～8 hours at 350 DEG C, just obtain the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous.
Three of object of the present invention is to provide the application of the carrier loaded nm of gold cyclohexane oxidation catalyst of above-mentioned multi-stage porous, this catalyst is applied to taking molecular oxygen as oxygen source, under solvent-free and initator exist, with cyclohexane and oxygen reaction synthesizing cyclohexanol and cyclohexanone, detailed process is as follows:
(1) by catalyst 30mg, cyclohexane 10mL is placed in 100mL inner liner polytetrafluoroethylene autoclave, and blowing air displacement gas reactor three times, then passes into air to 1MPa under room temperature; Autoclave is heated to 130 DEG C, stirs with the speed of 400rpm, react cooling after 3 hours, emit residual gas, use ethanol lysate, add excessive triphenyl phosphorus reduction, make the cyclohexyl hydroperoxide in product resolve into cyclohexanol and cyclohexanone, centrifugation goes out catalyst;
(2) after the catalyst of centrifugation is collected, use acetone cyclic washing, dry the catalyst reclaiming, carries out catalytic reaction by step (1) reaction condition with the catalyst of recovery, and catalyst can reaction repeated.
The present invention compared to the prior art, nm of gold or gold-palladium (silver) alloy good dispersion on carrier, be difficult for running off and reuniting, heteropoly acid has promoted the activity of noble metal composition simultaneously, cyclohexane conversion and KA oil are selectively improved simultaneously, the recovery experiment of catalyst shows, catalyst can be reused more than 5 times, there is no the active phenomenon declining.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1:0.5%Au-PMo
12(5)/AlP-SiO
2(load stabilization with phosphomolybdic acid nm of gold/aluminum phosphate-silica, gold loading 0.5%, with respect to carrier mass percent, Au/PMo
12mol ratio=5) preparation:
(1) the 2mM HAuCl of 21.2mL
4the aqueous solution adds phosphomolybdic acid 0.016g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 2mL, stirring reaction forms red nano gold colloid solution for 3～5 hours.
(2) boehmite 0.5g stirs lower and 6.7mL water mixing, is hydrolyzed after 0.5 hour, adds phosphoric acid 0.79g, adds N-stearyl propane diamine 0.56g after 1 hour, stirs and forms homogeneous phase solution A; 1.42g tetraethyl orthosilicate and 6.5mL water mix, and the P123 that adds 0.63g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the red nano gold colloid solution of being prepared by step (1) and step (2) form mixes, stir 20 hours, then slowly drip 25% (mass percent concentration, lower embodiment with) the TBAH aqueous solution to pH value is 8, obtains red gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst 0.5%Au-PMo
12(5)/AlP-SiO
2.
Embodiment 2:1%Au – PW
11v (5)/AlP-SiO
2(load one vanadium replaces phosphotungstic acid stabilized nanoscale gold/aluminum phosphate-silica, and gold loading 1%, with respect to carrier mass percent, Au/PW
11v mol ratio=5) preparation:
(1) the 2mM HAuCl of 42.4mL
4the aqueous solution adds a vanadium to replace phosphotungstic acid 0.046g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 8mL, stirring reaction forms red nano gold colloid solution for 3～5 hours and forms red nano gold colloid solution.
(2) boehmite 1g stirs lower and 12.5mL water mixing, is hydrolyzed after 0.5 hour, adds phosphatase 11 .58g, adds N-oil base propane diamine 1.34g after 1 hour, stirs and forms homogeneous phase solution A; 2.85g tetraethyl orthosilicate and 12.5mL water mix, and the P123 that adds 1.41g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the red nano gold colloid solution of being prepared by step (1) and step (2) form mixes, and stirs 20 hours, and then slowly dripping the 25% TBAH aqueous solution to pH value is 8, obtains red gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst 1%Au-PMo
12(5)/AlP-SiO
2.
Embodiment 3:1.5%Au – PW
10v
2(5)/AlP-SiO
2(load two vanadium replace phosphotungstic acid stabilized nanoscale gold/aluminum phosphate-silica, and gold loading 1.5%, with respect to carrier mass percent, Au/PW
10v
2mol ratio=5) preparation:
(1) the 2mM HAuCl of 31.8mL
4the aqueous solution adds two vanadium to replace phosphotungstic acid 0.033g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 3.8mL, stirring reaction forms red nano gold colloid solution for 3～5 hours and forms red nano gold colloid solution.
(2) boehmite 0.5g stirs lower and 7.3mL water mixing, is hydrolyzed after 0.5 hour, adds phosphoric acid 0.79g, adds N-stearyl propane diamine 0.71g after 1 hour, stirs and forms homogeneous phase solution A; 1.43g tetraethyl orthosilicate and 7.3mL water mix, and the P123 that adds 0.8g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the red nano gold colloid solution of being prepared by step (1) and step (2) form mixes, and stirs 20 hours, and then slowly dripping the 25% TBAH aqueous solution to pH value is 8, obtains red gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst 1.5%Au – PW
10v
2(5)/AlP-SiO
2.
Embodiment 4:(0.3%Au+0.3%Pd) – PMo
12(10)/AlP-SiO
2(load one vanadium replaces phosphotungstic acid stabilized nanoscale gold+palladium/aluminum phosphate-silica, and gold and palladium load capacity are respectively 0.3%, with respect to carrier mass percent, and (Au+Pd)/PMo
11v mol ratio=10) preparation:
(1) the 2mM HAuCl of 10.4mL
4the 2mMH of the aqueous solution and 10.4mL
2pdCl
4aqueous solution, adds phosphomolybdic acid 0.008g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 3.84mL, stirring reaction forms brown nm of gold palladium colloidal solution for 3～5 hours.
(2) boehmite 0.8g stirs lower and 10mL water mixing, is hydrolyzed after 0.5 hour, adds phosphatase 11 .28g, adds N-stearyl propane diamine 1.32g after 1 hour, stirs and forms homogeneous phase solution A; 2.28g tetraethyl orthosilicate and 10mL water mix, and the P123 that adds 1.09g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the brown nm of gold palladium colloidal solution of being prepared by step (1) and step (2) form mixes, stir 20 hours, then slowly dripping the 25% TBAH aqueous solution to pH value is 8, obtains brownish black gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst (0.3%Au+0.3%Pd) – PMo
12(10)/AlP-SiO
2.
Embodiment 5:(0.5%Au+0.5%Pd) – PW
11v (8)/AlP-SiO
2(load one vanadium replaces stabilization with phosphomolybdic acid nm of gold+palladium/aluminum phosphate-silica, and gold and palladium load capacity are respectively 0.5%, with respect to carrier mass percent, and (Au+Pd)/PMo
11v mol ratio=8) preparation:
(1) the 2mM HAuCl of 8.6mL
4the 2mMH of the aqueous solution and 8.6mL
2pdCl
4aqueous solution, adds a vanadium to replace phosphotungstic acid 0.012g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 3.2mL, stirring reaction forms brownish black nm of gold palladium colloidal solution for 3～5 hours.
(2) boehmite 0.4g stirs lower and 5mL water mixing, is hydrolyzed after 0.5 hour, adds phosphoric acid 0.64g, adds N-oil base propane diamine 0.7g after 1 hour, stirs and forms homogeneous phase solution A; 1.14g tetraethyl orthosilicate and 5mL water mix, and the P123 that adds 0.56g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the nm of gold palladium colloidal solution of being prepared by step (1) and step (2) form mixes, and stirs 20 hours, and then slowly dripping the 25% TBAH aqueous solution to pH value is 8, obtains gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst (0.5%Au+0.5%Pd) – PMo
11v (10)/AlP-SiO
2.
Embodiment 6:(0.7%Au+0.7%Ag) – PMo
12(10)/AlP-SiO
2(load stabilization with phosphomolybdic acid nm of gold+silver/aluminum phosphate-silica, golden and silver-colored load capacity is respectively 0.7%, with respect to carrier mass percent, (Au+Ag)/PMo
11v mol ratio=10) preparation:
(1) the 2mM HAuCl of 12mL
4the 2mMAgNO of the aqueous solution and 12mL
3aqueous solution, adds phosphomolybdic acid 0.02g, stirs and forms yellow solution, adds rapidly the NaBH of 0.1M under rapid stirring
4aqueous solution 4.5mL, stirring reaction forms brown nanometer gold silver colloidal solution for 3～5 hours.
(2) boehmite 0.56g stirs lower and 8mL water mixing, is hydrolyzed after 0.5 hour, adds phosphoric acid 0.90g, adds N-oil base propane diamine 0.98g after 1 hour, stirs and forms homogeneous phase solution A; 1.60g tetraethyl orthosilicate and 8mL water mix, and the P123 that adds 0.78g is template, regulate mixed solution to make pH=3 with 1MHCl solution, stir formation homogeneous phase solution B.A and B mix and blend are formed to colloidal sol for 2 hours.
(3) colloidal sol that the brown nanometer gold silver colloidal solution of being prepared by step (1) and step (2) form mixes, and stirs 20 hours, and then slowly dripping the 25% TBAH aqueous solution to pH value is 8, obtains gel.
(4) gel step (3) being obtained is transferred in 100mL band teflon-lined water heating kettle, is placed in baking oven, under 120 DEG C of hydrothermal conditions, reacts 48 hours.After cooling, solid collected by filtration, solid washs by deionized water, at 100 DEG C, dries.Then by the roasting 6 hours at 350 DEG C of dried solid, obtain catalyst (0.7%Au+0.7%Ag) – PMo
12(10)/AlP-SiO
2.
Embodiment 7: catalyst activity evaluation
Solvent-free catalytic oxidation of cyclohexane carries out in band teflon-lined 100mL autoclave, the catalyst that 30mg the present invention is made and 10mL cyclohexane are added in autoclave, after sealing, with air displacement gas reactor three times, then under normal temperature, passing into air to reactor pressure is 1MPa, make temperature rise to 130 DEG C by autoclave controller, mixing speed is 400rpm, react 3 hours, cooling, emit residual gas, ethanol lysate, add excessive triphenyl phosphorus reduction to make the cyclohexyl hydroperoxide in product resolve into cyclohexanol and cyclohexanone, centrifugation goes out catalyst.Reactant liquor gas chromatographic analysis, Shimadzu 2014C gas chromatograph, SE-30 capillary column, hydrogen flame detector, taking normal heptane as interior mark, calculating K A oil productive rate.
With (0.5%Au+0.5%Pd) – PW
11v (8)/AlP-SiO
2for example, by reacted catalyst, after centrifugation, wash and be dried with acetone, the catalyst of recovery is carried out to catalytic oxidation of cyclohexane reaction by embodiment 7 reaction conditions, catalyst circulates 5 times altogether, reaction result gas chromatographic analysis.
Table 1 catalyst activity rating
Table 2 (0.5%Au+0.5%Pd) – PW
11v (8)/AlP-SiO
2recycle activity rating five times
Claims (8)
1. the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous, it is characterized in that: it is a kind of heteropoly acid (HPA)-nano-noble metal super molecular compound that is carried on multistage mesoporous aluminum phosphate-silicon dioxide composite material, and its structural formula is: Au-HPA/AlPO
4-SiO
2.
2. the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous described in requiring 1 according to right profit, is characterized in that: described heteropoly acid is the one in Keggin type phosphorus molybdenum, phosphorus tungsten, phosphorus molybdenum one vanadium, phosphorus molybdenum two vanadium, phosphorus tungsten one vanadium and phosphorus tungsten two vanadium heteropoly acids.
3. the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous described in requiring 1 according to right profit, is characterized in that: described nano-noble-metal-loaded is single nm of gold, nanogold-silver alloy and nm of gold-palldium alloy.
4. the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous described in requiring 3 according to right profit, is characterized in that: described nano-noble metal content is 0.3～2.5% of carrier quality, the particle diameter of nano-noble metal is 1-20nm.
5. the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous described in requiring 1 according to right profit, is characterized in that: the mesoporous scope of described multistage mesoporous aluminum phosphate-silica complex carrier is 2-7nm, and the mole ratio of aluminum phosphate and silica is 1:1.
6. a preparation method for the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous as claimed in claim 1, is characterized in that comprising the step of following order:
(1) taking gold chloride as Jin Yuan, silver nitrate is silver-colored source, the acid of chlorine palladium is for preparing heteropoly acid stabilized nanoscale precious metal colloid solution in palladium source: by the gold chloride of the gold chloride of single gold chloride or 1:1 mixed in molar ratio and silver nitrate or 1:1 mixed in molar ratio and the acid of chlorine palladium, add deionized water and be made into the solution that concentration is 2～5mM, add again solid heteropoly acid, stir lower mixing, wherein, the mol ratio of noble metal and heteropoly acid is 5/1～15/1; After 1 hour, add the NaBH of excessive 0.1M
4solution, adds NaBH
4mole is 3～10 times of noble metal mole in solution, and stirring reaction 3～5 hours under room temperature, makes heteropoly acid stabilized nanoscale precious metal colloid solution;
(2) taking boehmite as aluminium source, by boehmite and phosphoric acid, water, N-stearyl propane diamine or N-oil base propane diamine by 1Al:1P:0.06～0.25N-stearyl propane diamine or N-oil base propane diamine: the mixed in molar ratio of 50 water becomes solution A; Taking tetraethyl orthosilicate as silicon source, tetraethyl orthosilicate, triblock polymer P123, water are pressed to 1Si:0.016P123:50～100H
2the mixed in molar ratio of O, with 1M salt acid for adjusting pH be 3 formation solution B; Solution A and solution B are mixed and stirred and within 2 hours, form even colloidal sol;
(3) step (2) gained colloidal sol is slowly added in step (1) gained heteropoly acid stabilized nanoscale precious metal colloid solution, under room temperature, stir 20～36 hours, dripping mass percent concentration again and be 25% the TBAH aqueous solution, to regulate pH value be 8～9, continue to stir 2～4 hours, form gel;
(4) previous step gained gel is transferred in water heating kettle to hydrothermal treatment consists 48 hours at 120 DEG C, the solid after then filtering, wash by deionized water, dry at 100 DEG C again, calcine 4～8 hours at 350 DEG C, just obtain the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous.
7. the preparation method of the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous according to claim 6, is characterized in that: described heteropoly acid is the one in Keggin type phosphorus molybdenum, phosphorus tungsten, phosphorus molybdenum one vanadium, phosphorus molybdenum two vanadium, phosphorus tungsten one vanadium and phosphorus tungsten two vanadium heteropoly acids.
8. the application of the carrier loaded nm of gold cyclohexane oxidation catalyst of multi-stage porous as claimed in claim 1, it is characterized in that: be applied to taking molecular oxygen as oxygen source, under solvent-free and initator exist, with cyclohexane and oxygen reaction synthesizing cyclohexanol and cyclohexanone, detailed process is as follows:
(1) by catalyst 30mg, cyclohexane 10mL is placed in 100mL inner liner polytetrafluoroethylene autoclave, and blowing air displacement gas reactor three times, then passes into air to 1MPa under room temperature; Autoclave is heated to 130 DEG C, stirs with the speed of 400rpm, react cooling after 3 hours, emit residual gas, use ethanol lysate, add excessive triphenyl phosphorus reduction, make the cyclohexyl hydroperoxide in product resolve into cyclohexanol and cyclohexanone, centrifugation goes out catalyst;
(2) after the catalyst of centrifugation is collected, use acetone cyclic washing, dry the catalyst reclaiming, carries out catalytic reaction by step (1) reaction condition with the catalyst of recovery, and catalyst can reaction repeated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105327717A (en) * | 2015-12-03 | 2016-02-17 | 湖南科技大学 | Nano-gold cyclohexane oxidation catalyst encapsulated through SiO2 and mesoporous TiO2 hollow microspheres and preparation and application of nano-gold cyclohexane oxidation catalyst |
| CN109420526A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of braiding mesoporous polymer carries silver catalyst and the preparation method and application thereof |
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| CN101817733A (en) * | 2009-11-02 | 2010-09-01 | 兰州理工大学 | Method for preparing cyclohexanone by oxidizing cyclohexane |
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| US20050222452A1 (en) * | 2004-03-31 | 2005-10-06 | Council Of Scientific And Industrial Research | Process for preparing dioxy-functionalized propane compounds |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327717A (en) * | 2015-12-03 | 2016-02-17 | 湖南科技大学 | Nano-gold cyclohexane oxidation catalyst encapsulated through SiO2 and mesoporous TiO2 hollow microspheres and preparation and application of nano-gold cyclohexane oxidation catalyst |
| CN109420526A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of braiding mesoporous polymer carries silver catalyst and the preparation method and application thereof |
| CN109420526B (en) * | 2017-08-21 | 2021-06-15 | 中国科学院大连化学物理研究所 | Woven mesoporous polymer silver-loaded catalyst and preparation method and application thereof |
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