CN104667913A - Macroporous aluminum oxide assembled nano metal catalyst as well as preparation and application to methanol liquid-phase catalytic reaction - Google Patents
Macroporous aluminum oxide assembled nano metal catalyst as well as preparation and application to methanol liquid-phase catalytic reaction Download PDFInfo
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Abstract
The invention provides a macroporous aluminum oxide assembled nano metal catalyst as well as preparation and application to a methanol liquid-phase catalytic reaction and belongs to the technical field of nano metal catalysis and fine chemical engineering. Macroporous aluminum oxide is prepared by taking pseudo-boehmite as raw material and polyethylene glycol as a template agent through adopting an ultrasonic-hydrothermal method; and then the macroporous aluminum oxide is used as a carrier so that single-component metal Pd and Au or a double-component metal Pd-Au catalytic active component is assembled in the macroporous aluminum oxide under the effect of ultrasonic waves to prepare a double-function catalyst with a selective oxidization performance and an acid performance. The double-function catalyst has a very good catalytic performance in a methanol selective oxidation coupled methanol condensation and esterification reaction to synthesize methylal and methyl formate, and has a very important industrial application value.
Description
Technical field
The present invention relates to a kind of macroporous aluminium oxide assemble nanometer metallic catalyst, preparation and for methanol solution phase catalytic reaction, belong to nano metal catalysis and technical field of fine.
Background technology
Along with the production capacity surplus of methyl alcohol, the Downstream Products of Methanol that exploitation has high added value has great importance.In numerous Downstream Products of Methanol, dimethoxym ethane (chemical name is dimethoxymethane) and methyl formate are the high added value methyl alcohol downstream green chemical products enjoying people to pay close attention to.Dimethoxym ethane has low toxicity, low boiling, good dissolubility, the fields such as medicine, cosmetics, automobile are widely used in, the toxic solvents such as alternative benzene, toluene, and when dimethoxym ethane adds as diesel fuel additives, effectively can improve the combustibility of engine, reducing HC, CO content in emission, reduce environmental pollution, is a kind of well diesel fuel additives.Methyl formate is a kind of important organic synthesis intermediate, has been widely used in the fields such as the synthesis of acetate fiber, medicine, agricultural chemicals.
The production of current dimethoxym ethane has two-step method and one-step method, and two-step method first methanol oxidation is generated formaldehyde, and then formaldehyde and carbinol condensation obtain.Two-step mode technique comparative maturity, but technological process more complicated, waste liquid are many, production cost is high.One-step method is under the effect of bifunctional catalyst, the selective oxidation of methyl alcohol and condensation is coupled, and realizes methyl alcohol one-step synthesis dimethoxym ethane, and therefore one-step method has the advantages such as technological process is simple.The production of methyl formate has methanol esterification method, methanol dehydrogenation method, methanol hydroxylethyl etc.Methanol esterification method is exactly be first formic acid by methanol oxidation, and then formic acid and methyl alcohol carry out esterification and obtains.The relatively synthesis technique of Methanol dimethoxym ethane and methyl formate, they have a common feature, be exactly that methyl alcohol is wanted first under the selective oxidation active component effect of catalyst, there is Selective Oxidation, generate formaldehyde or formic acid, then under the acid active component effect of catalyst, carry out condensation, esterification, and then generate dimethoxym ethane and methyl formate.
In recent years, it is found that some catalyst can make the selective oxidation of methyl alcohol and catalyzing and condensing (or esterification) reaction be coupled, by methyl alcohol one-step synthesis dimethoxym ethane and methyl formate.As discoveries such as V.V.Kaichev, be raw material with methyl alcohol, adopt V
2o
5/ TiO
2catalyst system, at methyl alcohol: O
2: the mol ratio of He is under the reaction condition of 1:1:23, a step can generate dimethoxym ethane and methyl formate (V.V.Kaichev, G.Ya.Popova, Yu.A.Chesalov, A.A.Saraev, D.Y.Zemlyanov, S.A.Beloshapkin A.Knop-Gericke, R.Schlogl, T.V.Andrushkevich, V.I.Bukhtiyarov.Selective oxidation of methanol to form dimethoxymethane and methyl formate over a monolayer V
2o
5/ TiO
2catalyst.Journal of Catalysis, 2014,311:59-70).Chinese patent CN 103537301A has prepared the V having the auxiliary agents such as vanadium, titanium, sulphur, strontium
2o
5-TiO
2catalyst, loads fixed bed reactors, after oxygen and inert gas activation, passes into methanol gas, oxygen, inert gas, obtains the overall selectivity of high methanol conversion and dimethoxym ethane and methyl formate after reaction.But these catalytic reactions are all the gas-solid reactions carried out in fixed bed reactors, the methanol gas concentration of charging is lower (being generally about 5%), and in course of reaction, therefore have a large amount of gas to recycle, observable index is higher.Meanwhile, the temperature also bad control of gas-solid catalytic reaction, the too high meeting of reaction temperature causes selective decline.If by precious metals pd good for selective oxidation of methanol performance, Au isoreactivity component, be assembled in and have in acid macroporous oxide material, prepare the catalyst of some novel methyl alcohol liquid phase catalytic cracking dimethoxym ethanes and methyl formate, when then can avoid adopting fixed bed reactors, the circulation of a large amount of gas in gas-solid reaction technique, meanwhile, the reaction temperature of liquid-phase catalysis also controls than being easier to, and this is very favorable to raising the selective of product.
Recently, we adopt ultrasonic technology to prepare fast to have mesoporous SiO
2the meso-SiO of shell structurre
2@Fe
3o
4microballoon (Hongfei Liu, Shengfu Ji, Hao Yang, Huan Zhang, Mi Tang.Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO
2@Fe
3o
4microspheres with enhanced mesoporous structure.Ultrasonics Sonochemistry.2014,21:505-512), and in the γ-AlOOH hole with meso-hole structure, can even assemble nanometer particle Pd catalytic active component (YANG Hao, JI ShengFu, LIU XueFei, ZHANG DanNi & SHI Da.Magnetically recyclable Pd/ γ-AlOOH@Fe
3o
4catalysts and their catalytic performance for the Heck coupling reaction.Science China Chemistry, 2014,57 (6): 866-872).Based on these research work bases, the present invention for raw material, take polyethylene glycol as template with the boehmite of cheapness, adopts ultrasonic wave-hydro-thermal method to prepare macropore alumina supporter.Due to the cavitation of ultrasonic wave uniqueness, the bubble that in preparation process, solution is formed breaks instantaneously, can form the environment of the high temperature of a local, high pressure and ultrafast cooling, thus can prepare macroporous aluminium oxide in inside, hole.Then take macroporous aluminium oxide as carrier, respectively by catalytic active component such as single component metal Pd, Au or two-component metal Pd-Au, be assembled in macroporous aluminium oxide hole under ul-trasonic irradiation, prepare nano metal/catalyst macropore alumina agent.
Owing to have employed ultrasonic technology in the present invention, make to be assembled in nano Pd particle, Au, Pd-Au particle that the metal active constituents such as Pd, Au, the Pd-Au in macroporous aluminium oxide hole define high dispersive, there is extraordinary methyl alcohol liquid phase selective oxidizing energy; Meanwhile, macroporous aluminium oxide surface has abundant acid site, can catalyzing and condensing or esterification, and then is coupled, the catalytic selective oxidation of methyl alcohol and catalyzing and condensing (or esterification) reaction by methyl alcohol one-step synthesis dimethoxym ethane and methyl formate.Therefore nano metal/catalyst macropore alumina agent of preparing of the present invention, both formaldehyde (formic acid) is generated to methyl alcohol liquid-phase selective oxidation and have good catalytic action, having good catalytic action to the formaldehyde (formic acid) generated in reaction and the further condensation of methyl alcohol (esterification) again, is the bifunctional catalyst that one has selective oxidation of methanol performance and carbinol condensation (esterification) performance.
Nano metal/macroporous aluminium oxide bifunctional catalyst prepared by the inventive method, can make methyl alcohol one step be catalytically conveted to dimethoxym ethane and methyl formate, and technological process is simple, easy to operate, therefore has important industrial application value.
Summary of the invention
The object of the present invention is to provide a kind of bifunctional catalyst and the preparation method and application that methyl alcohol one step are catalytically conveted to dimethoxym ethane and methyl formate.
The present invention first with the boehmite of cheapness for raw material, take polyethylene glycol as template, adopt ultrasonic wave-hydro-thermal method prepare macroporous aluminium oxide; Then be carrier with macroporous aluminium oxide, respectively by catalytic active component such as single component metal Pd, Au or two-component metal Pd-Au, be assembled under ul-trasonic irradiation in macroporous aluminium oxide hole, prepare and nano metal/macroporous aluminium oxide bifunctional catalyst that dimethoxym ethane and methyl formate have fine catalytic performance is catalytically conveted to methyl alcohol one step.
Macroporous aluminium oxide assemble nanometer metallic catalyst, is characterized in that, is the catalytic active component such as carrier, single component metal Pd, Au or two-component metal Pd-Au, is assembled in macroporous aluminium oxide hole under ul-trasonic irradiation with macroporous aluminium oxide.
The above-mentioned nano metal of the present invention/macroporous aluminium oxide bifunctional catalyst adopts and comprises the preparation of following method step:
(1) macroporous aluminium oxide preparation: boehmite is joined in the salpeter solution of 0.5M ~ 1.5M, make Al
2o
3mass content is the solution of 14.8% ~ 25.9%, is designated as A liquid; Polyethylene glycol is dissolved in ethanol, makes the polyglycol solution that polyethylene glycol mass content is 12.0% ~ 16.7%, be designated as B liquid; Under 40 DEG C of stirring conditions, B drop is added in A liquid, after fully stirring, under 150W ~ 250W ultrasonic power, ultrasonic 30min ~ 50min, then puts into autoclave by mixed liquor, at 120 DEG C ~ 150 DEG C, hydrothermal crystallizing 6 ~ 8 hours, naturally cool, wash neutrality, vacuum drying with deionized water and ethanol respectively, last 550 DEG C of roastings 6 hours, be obtained macropore alumina supporter;
(2) nano metal/macroporous aluminium oxide bifunctional catalyst preparation: take palladium bichloride or palladium or palladium nitrate and be dissolved in deionized water, make Pd solution; Taking gold chloride is dissolved in deionized water, makes Au solution; Respectively by Pd solution or/and Au solution adds in macroporous aluminium oxide solution, after fully stirring, ultrasonic 40min ~ 60min under 100W ~ 150W ultrasonic power, makes metal component be assembled in macroporous aluminium oxide hole, vacuum drying, N
2200 DEG C ~ 300 DEG C roastings 6 ~ 8 hours under atmosphere, namely obtain nano metal/macroporous aluminium oxide bifunctional catalyst.
Wherein preferably the mass content of Pd element in whole catalyst is the mass content of 1.1wt% ~ 4.58wt%, Au element in whole catalyst is 1.29wt% ~ 5.04wt%.
Above-mentioned polyethylene glycol is preferably PEG-1500.Vacuum drying in step (1) and (2) preferably 50 DEG C of dryings 8 hours.
The present invention adopts the nano metal of preparation/macroporous aluminium oxide bifunctional catalyst to be applied to methyl alcohol liquid-phase selective oxidation coupling and catalyzing condensation (esterification) reaction, dimethoxym ethane and methyl formate by methyl alcohol one-step synthesis.Catalytic reaction is carried out in autoclave stirred reactor, and liquid methanol is raw material, adds nano metal/macroporous aluminium oxide bifunctional catalyst, is filled with O
2, be 80 DEG C ~ 140 DEG C in reaction temperature, the reaction time is react under the condition of 12 ~ 18 hours, obtains dimethoxym ethane and methyl formate.Result shows that the nano metal/macroporous aluminium oxide bifunctional catalyst prepared has the overall selectivity of good methanol conversion and dimethoxym ethane and methyl formate, and the active component of catalyst does not run off, and has good stability.
Nano metal prepared by the present invention/catalyst macropore alumina agent has following remarkable advantage:
(1) in the preparation process of macropore alumina supporter, owing to have employed the integrated processes of ultrasonic wave-hydro-thermal, utilize the microenvironment of hyperacoustic localized hyperthermia, high pressure and ultrafast cooling, the aluminium oxide of macropore can be prepared, provide and there is carrier that is acid, that easily assemble catalytic active component.
(2) in the nano metal prepared/catalyst macropore alumina agent, catalytic active component Pd, Au, Pd-Au etc. are in the hole of the aluminium oxide being assembled in macropore, therefore the good dispersion of catalytic active component, this not only increases the activity of catalyst, and gathering and the loss of catalytic active component in course of reaction can be avoided, greatly improve the stability of catalyst.
(3) nano metal prepared/catalyst macropore alumina agent, selective oxidation of methanol and condensation, esterification can be coupled, methyl alcohol one step is made to be catalytically conveted to dimethoxym ethane and methyl formate, there is good conversion ratio and selective, and technological process is simple, easy to operate, therefore there is important industrial application value.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1
(1) 20.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 0.5M nitric acid of 80.0g, make Al
2o
3mass content is the solution of 14.8wt%, is designated as A1 liquid; Take 3.0g polyethylene glycol (PEG-1500), be dissolved in 22.0g ethanol, make the polyglycol solution that polyethylene glycol mass content is 12.0%, be designated as B1 liquid.Under 40 DEG C of stirring conditions, B1 drop is added in A1 liquid, after fully stirring, under 150W ultrasonic power, ultrasonic 50min, then puts into autoclave by mixed liquor, at 120 DEG C, hydrothermal crystallizing 6 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT1 carrier.
(2) PdCl of 2.6g is taken
2, be dissolved in 97.4g deionized water, make the Pd solution that Pd mass content is 1.56wt%, be designated as C1 solution.Take the ZT1 carrier that 10.0g is obtained, add the C1 solution of 20.0g, after fully stirring, under 100W ultrasonic power, ultrasonic 60min, makes metal Pd component be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 50 DEG C, at N
2the lower 200 DEG C of roastings of atmosphere 6 hours, are obtained 3.01wt%Pd/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.4mol, then add the 3.01wt%Pd/ catalyst macropore alumina agent that Pd content is 5mmol, be filled with O
2to 0.3MPa, then react 16 hours at 90 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 66.5%, and the selective of dimethoxym ethane is 73.2%, and the selective of methyl formate is 22.6%, and the overall selectivity of dimethoxym ethane and methyl formate is 95.8%.
Embodiment 2
(1) 30.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 1.0M nitric acid of 70.0g, make Al
2o
3mass content is the solution of 22.2wt%, is designated as A2 liquid; Take 4.0g polyethylene glycol (PEG-1500), be dissolved in 26.0g ethanol, make the polyglycol solution that polyethylene glycol mass content is 13.3%, be designated as B2 liquid.Under 40 DEG C of stirring conditions, B2 drop is added in A2 liquid, after fully stirring, under 200W ultrasonic power, ultrasonic 40min, then puts into autoclave by mixed liquor, at 130 DEG C, hydrothermal crystallizing 7 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT2 carrier.
(2) Pd (NO of 2.3g is taken
3)
2, be dissolved in 47.7g deionized water, make the Pd solution that Pd mass content is 2.12wt%, be designated as C2 solution.Take the ZT2 carrier that 15.0g is obtained, add the C2 solution of 25.0g, after fully stirring, under 120W ultrasonic power, ultrasonic 50min, makes metal Pd component be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 50 DEG C, at N
2the lower 250 DEG C of roastings of atmosphere 5 hours, are obtained 3.41wt%Pd/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.5mol, then add the 3.41wt%Pd/ catalyst macropore alumina agent that Pd content is 6mmol, be filled with O
2to 0.4MPa, then react 18 hours at 80 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 62.3%, and the selective of dimethoxym ethane is 79.1%, and the selective of methyl formate is 15.2%, and the overall selectivity of dimethoxym ethane and methyl formate is 94.3%.
Embodiment 3
(1) 35.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 1.5M nitric acid of 65.0g, make Al
2o
3mass content is the solution of 25.9wt%, is designated as A3 liquid; Take 5.0g polyethylene glycol (PEG-1500), be dissolved in 25.0g ethanol, make the polyglycol solution that polyethylene glycol mass content is 16.7%, be designated as B3 liquid.Under 40 DEG C of stirring conditions, B3 drop is added in A3 liquid, after fully stirring, under 250W ultrasonic power, ultrasonic 30min, then puts into autoclave by mixed liquor, at 150 DEG C, hydrothermal crystallizing 8 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT3 carrier.
(2) Pd (CH of 3.4g is taken
3cOO)
2, be dissolved in 96.6g deionized water, make the Pd solution that Pd mass content is 1.6wt%, be designated as solution C3.Take the ZT3 carrier that 10.0g is obtained, add the solution C3 of 30.0g, after fully stirring, under 150W ultrasonic power, ultrasonic 40min, makes metal Pd component be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 50 DEG C, at N
2the lower 300 DEG C of roastings of atmosphere 6 hours, are obtained 4.58wt%Pd/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.3mol, then add the 4.58wt%Pd/ catalyst macropore alumina agent that Pd content is 4mmol, be filled with O
2to 0.3MPa, then react 14 hours at 110 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 85.2%, and the selective of dimethoxym ethane is 31.7%, and the selective of methyl formate is 60.9%, and the overall selectivity of dimethoxym ethane and methyl formate is 92.6%.
Embodiment 4
(1) 25.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 0.5M nitric acid of 75.0g, make Al
2o
3mass content is the solution of 18.5wt%, is designated as A4 liquid; Take 3.5g polyethylene glycol (PEG-1500), be dissolved in 21.5g ethanol, make the polyglycol solution that polyethylene glycol mass content is 14.0%, be designated as B4 liquid.Under 40 DEG C of stirring conditions, B4 drop is added in A4 liquid, after fully stirring, under 200W ultrasonic power, ultrasonic 35min, then puts into autoclave by mixed liquor, at 135 DEG C, hydrothermal crystallizing 6 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT4 carrier.
(2) HAuCl of 5.1g is taken
4, be dissolved in 144.9g deionized water, make the Au solution that Au mass content is 2.95wt%, be designated as D4 solution.Take the ZT4 carrier that 10.0g is obtained, add the D4 solution of 18.0g, after fully stirring, under 100W ultrasonic power, ultrasonic 50min, makes metal A u component be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 80 DEG C, at N
2the lower 250 DEG C of roastings of atmosphere 7 hours, are obtained 2.56wt%Au/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.3mol, then add the 2.56wt%Au/ catalyst macropore alumina agent that Au content is 5mmol, be filled with O
2to 0.5MPa, then react 18 hours at 120 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 75.5%, and the selective of dimethoxym ethane is 45.2%, and the selective of methyl formate is 51.0%, and the overall selectivity of dimethoxym ethane and methyl formate is 96.2%.
Embodiment 5
(1) 28.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 1.0M nitric acid of 72.0g, make Al
2o
3mass content is the solution of 20.72wt%, is designated as A5 liquid; Take 4.5g polyethylene glycol (PEG-1500), be dissolved in 25.5g ethanol, make the polyglycol solution that polyethylene glycol mass content is 15.0%, be designated as B5 liquid.Under 40 DEG C of stirring conditions, B5 drop is added in A5 liquid, after fully stirring, under 150W ultrasonic power, ultrasonic 50min, then puts into autoclave by mixed liquor, at 140 DEG C, hydrothermal crystallizing 6 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT5 carrier.
(2) PdCl of 1.8g is taken
2, be dissolved in 98.2g deionized water, make the Pd solution that Pd mass content is 1.1wt%, be designated as C5 solution.Take the HAuCl of 6.8g
4, be dissolved in 93.2g deionized water, make the Au solution that Au mass content is 3.94wt%, be designated as D5 solution.Take the macropore alumina supporter ZT5 that 10.0g is obtained, add the Pd solution (C5 solution) of 10.0g, add the Au solution (D5 solution) of 10.0g again, after abundant stirring, under 150W ultrasonic power, ultrasonic 60min, makes the component such as metal Pd, Au be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 80 DEG C, N
2250 DEG C of roastings 6 hours under atmosphere, be obtained 1.1wt%Pd-3.79wt%Au/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.3mol, then add the 1.1wt%Pd-3.79wt%Au/ catalyst macropore alumina agent that Pd and Au content sum is 5mmol, be filled with O
2to 0.3MPa, then react 14 hours at 130 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 91.6%, and the selective of dimethoxym ethane is 27.4%, and the selective of methyl formate is 70.2%, and the overall selectivity of dimethoxym ethane and methyl formate is 97.6%.
Embodiment 6
(1) 32.0g boehmite (Al is taken
2o
3xH
2o, Al
2o
3mass content is 74%) be dissolved in the 1.5M nitric acid of 68.0g, make Al
2o
3mass content is the solution of 23.68wt%, is designated as A6 liquid; Take 4.2g polyethylene glycol (PEG-1500), be dissolved in 25.8g ethanol, make the polyglycol solution that polyethylene glycol mass content is 14.0%, be designated as B6 liquid.Under 40 DEG C of stirring conditions, B6 drop is added in A6 liquid, after fully stirring, under 200W ultrasonic power, ultrasonic 40min, then puts into autoclave by mixed liquor, at 150 DEG C, hydrothermal crystallizing 7 hours, naturally after cooling, washs neutrality with deionized water and ethanol respectively, vacuum drying 8 hours at 50 DEG C, last 550 DEG C of roastings 6 hours, be obtained macroporous aluminium oxide, be designated as ZT6 carrier.
(2) PdCl of 5.3g is taken
2, be dissolved in 94.7g deionized water, make the Pd solution that Pd mass content is 3.18wt%, be designated as C6 solution.Take the HAuCl of 3.4g
4, be dissolved in 146.6g deionized water, make the Au solution that Au mass content is 1.31wt%, be designated as D6 solution.Take the macropore alumina supporter ZT6 that 10.0g is obtained, add the Pd solution (C6 solution) of 10.0g, add the Au solution (D6 solution) of 10.0g again, after abundant stirring, under 150W ultrasonic power, ultrasonic 60min, makes the component such as metal Pd, Au be assembled in macroporous aluminium oxide hole.After drying, vacuum drying 8 hours at 80 DEG C, N
2250 DEG C of roastings 6 hours under atmosphere, be obtained 3.08wt%Pd-1.29wt%Au/ catalyst macropore alumina agent.
(3) in 100ml autoclave stirred reactor, add the methyl alcohol of 0.5mol, then add the 3.08wt%Pd-1.29wt%Au/ catalyst macropore alumina agent that Pd and Au content sum is 6mmol, be filled with O
2to 0.5MPa, then react 12 hours at 140 DEG C.After having reacted, determined by chromatography, the conversion ratio of methyl alcohol is 93.8%, and the selective of dimethoxym ethane is 23.1%, and the selective of methyl formate is 72.6%, and the overall selectivity of dimethoxym ethane and methyl formate is 95.7%.
Claims (6)
1. macroporous aluminium oxide assemble nanometer metallic catalyst, is characterized in that, take macroporous aluminium oxide as carrier, and single component metal Pd, Au or two-component metal Pd-Au catalytic active component, be assembled in macroporous aluminium oxide hole under ul-trasonic irradiation.
2. according to the macroporous aluminium oxide assemble nanometer metallic catalyst of claim 1, it is characterized in that, the mass content of Pd element in whole catalyst is the mass content of 1.1wt% ~ 4.58wt%, Au element in whole catalyst is 1.29wt% ~ 5.04wt%.
3. the method for the macroporous aluminium oxide assemble nanometer metallic catalyst of preparation described in claim 1 or 2, is characterized in that, comprise the following steps: prepared by (1) macroporous aluminium oxide: joined by boehmite in the salpeter solution of 0.5M ~ 1.5M, make Al
2o
3mass content is the solution of 14.8% ~ 25.9%, is designated as A liquid; Polyethylene glycol is dissolved in ethanol, makes the polyglycol solution that polyethylene glycol mass content is 12.0% ~ 16.7%, be designated as B liquid; Under 40 DEG C of stirring conditions, B drop is added in A liquid, after fully stirring, under 150W ~ 250W ultrasonic power, ultrasonic 30min ~ 50min, then puts into autoclave by mixed liquor, at 120 DEG C ~ 150 DEG C, hydrothermal crystallizing 6 ~ 8 hours, naturally cool, wash neutrality, vacuum drying with deionized water and ethanol respectively, last 550 DEG C of roastings 6 hours, be obtained macropore alumina supporter;
(2) nano metal/macroporous aluminium oxide bifunctional catalyst preparation: take palladium bichloride or palladium or palladium nitrate and be dissolved in deionized water, make Pd solution; Taking gold chloride is dissolved in deionized water, makes Au solution; Respectively by Pd solution or/and Au solution adds in macroporous aluminium oxide solution, after fully stirring, ultrasonic 40min ~ 60min under 100W ~ 150W ultrasonic power, makes metal component be assembled in macroporous aluminium oxide hole, vacuum drying, N
2200 DEG C ~ 300 DEG C roastings 6 ~ 8 hours under atmosphere, namely obtain nano metal/macroporous aluminium oxide bifunctional catalyst.
4. according to the method for claim 3, it is characterized in that, above-mentioned polyethylene glycol is preferably PEG-1500.
5. according to the method for claim 3, it is characterized in that, the preferably 50 DEG C of dryings 8 hours of the vacuum drying in step (1) and (2).
6. the macroporous aluminium oxide assemble nanometer metallic catalyst described in claim 1 or 2 is used for the coupling and catalyzing condensation of methyl alcohol liquid-phase selective oxidation and esterification, by methyl alcohol one-step synthesis dimethoxym ethane and methyl formate.
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| CN105521798A (en) * | 2016-01-06 | 2016-04-27 | 北京化工大学 | Magnetic bifunctional catalyst, preparation method therefor and application of magnetic bifunctional catalyst in methanol catalyzed reaction |
| CN107185532A (en) * | 2017-05-11 | 2017-09-22 | 北京化工大学 | A kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and for ethanol phase catalytic reaction |
| CN108855023A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of preparation method and denitrating technique of catalyst for denitrating flue gas |
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| CN104399536A (en) * | 2014-11-28 | 2015-03-11 | 华东理工大学 | Eutectic crystal, single atomic dispersion palladium catalyst containing eutectic crystal, preparation method and application |
| CN104399536B (en) * | 2014-11-28 | 2019-08-30 | 华东理工大学 | A kind of eutectic, containing its single atomic dispersion palladium catalyst, preparation method and application |
| CN105521798A (en) * | 2016-01-06 | 2016-04-27 | 北京化工大学 | Magnetic bifunctional catalyst, preparation method therefor and application of magnetic bifunctional catalyst in methanol catalyzed reaction |
| CN105521798B (en) * | 2016-01-06 | 2017-12-15 | 北京化工大学 | A kind of magnetic bifunctional catalyst, prepare and reacted for methanol oxidation |
| CN107185532A (en) * | 2017-05-11 | 2017-09-22 | 北京化工大学 | A kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and for ethanol phase catalytic reaction |
| CN108855023A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of preparation method and denitrating technique of catalyst for denitrating flue gas |
| CN107185532B (en) * | 2017-05-11 | 2020-05-19 | 北京化工大学 | Macroporous titanium dioxide assembled nano metal catalyst, preparation and application in ethanol liquid phase catalytic reaction |
| CN112973681A (en) * | 2019-12-16 | 2021-06-18 | 中国科学院大连化学物理研究所 | Application of metal nanocluster catalyst in preparation of acetal by alcohol one-step method |
| CN112973681B (en) * | 2019-12-16 | 2022-11-08 | 中国科学院大连化学物理研究所 | Application of metal nanocluster catalyst in preparation of acetal by alcohol one-step method |
| CN111905758A (en) * | 2020-08-18 | 2020-11-10 | 厦门大学 | Gold-based catalyst, preparation method and application thereof |
| CN111905758B (en) * | 2020-08-18 | 2021-10-01 | 厦门大学 | Gold-based catalyst, preparation method and application thereof |
| CN113546620A (en) * | 2021-07-22 | 2021-10-26 | 山西大学 | Palladium oxide supported zinc-based catalyst and preparation method and application thereof |
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