CN109954500A - A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application - Google Patents
A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention provides a kind of copper-based compound membranous type hydrogenation catalysts of skeleton, in catalytic process, from the hydrogen flowed out in catalytic bed by the palladium UF membrane being coated on outside catalyst, hydrogen penetrates through palladium film, and then the hydrogen of high-purity is obtained from film side, so that hydrogen can be with direct reuse.Palladium film stops the reactants such as lighter hydrocarbons, esters and alcohols to pass through simultaneously, these reactants flow out together with product from catalyst bed lower part, and reactor outlet has obtained oxalate and its hydrogenation products methyl glycollate.
Description
Technical field
The present invention relates to catalyst technical fields, belong to a kind of adding for methyl glycollate for prepared by dimethyl oxalate plus hydrogen
Hydrogen catalyst.
Background technique
Methyl glycollate is colourless transparent liquid, molecular formula C3H6O3, it is a kind of important chemical intermediate and solvent,
It is widely used in the technical fields such as chemical industry, pesticide, medicine, dyestuff.The preparation process of most common methyl glycollate has
Formaldehyde and Formaldehyde Radical addition process, chloroactic acid method and Hydrogenation of Dimethyl Oxalate method.
Formaldehyde and Formaldehyde Radical addition process are formaldehyde and dimethoxym ethane under the action of peroxide catalyst, generate ethyl alcohol
Sour methyl esters, this kind of technological process of production is simple, easily operated, but peroxidating corrosivity with higher, so to reaction
The corrosion-resistant requirement of instrument is very high, and side reaction is more in the production technology, leads to containing for the methyl glycollate being prepared
It measures lower.
Chloroactic acid method is to mix monoxone with caustic soda to generate glycolic, then glycolic and methanol and strong sulfuric acid response
Methyl glycollate is generated, although chloroactic acid method obtains methyl glycollate, yield is higher, it is seriously polluted in preparation process, and work
The aborning wastewater treatment difficulty of skill is big, and chloride ion is also often accompanied by product ethanol acid methyl esters, and separation is also more tired
It is difficult.
Hydrogenation of Dimethyl Oxalate method be dimethyl oxalate under the effect of the catalyst, reacted with high pressure hydrogen, generate ethyl alcohol
Sour methyl esters, production technology pollution is small, and the yield of methyl glycollate is high, is production glycolic first most green, environmentally friendly at present
The technique of ester.In Hydrogenation of Dimethyl Oxalate method technique, catalyst plays the role of vital, directly influences ethyl alcohol
The yield and purity of sour methyl esters.Traditional catalyst use silver catalyst, but due to silver it is expensive, limit its industry and answer
With.
Skeleton catalyst is also known as Reni catalyst, is a kind of hydrogenation catalyst with higher catalytic activity.Skeleton catalysis
Agent is that the metal Yu aluminium or silicon of catalytic action form ontology alloy by, later again leaches aluminium and silicon with sodium hydroxide, is formed
Skeleton catalyst with biggish specific surface area and catalytic activity.
Since skeleton catalyst has above advantages, so it is used in Hydrogenation of Dimethyl Oxalate technique.In for example,
State patent document CN101254466A discloses a kind of load type Reni catalyst preparation method, which discloses
The mixture of the metal outer aluminium coating of thunder Buddhist nun's skeleton catalyst, aluminium alloy or aluminium will be formed, high temperature melts aluminium, but protects
The metal for holding thunder Buddhist nun's skeleton catalyst does not melt, cold extraction, using naoh treatment, obtains load type Reni catalyst, and public
It is nickel, copper, iron, chromium, silver or platinum that the metal of thunder Buddhist nun's skeleton catalyst can be formed by, which having opened, aluminium alloy be aluminium and nickel, copper, cobalt, iron or
The formation such as platinum.Above-mentioned catalyst has preferable high active of hydrogenation catalysis, long catalytic life.But above patent document discloses
The gas-phase product that is generated during catalysis of load type Reni catalyst, such as low molecular weight lighter hydrocarbons, can and hydrogen mixing, lead
Causing the partial pressure of hydrogen in circulation loop reduces, and influences hydrogenation efficiency, meanwhile, the hydrogen discharged in hydrogenation process can not recycle,
In addition separator must be set, could be used after processing, increase the cost of technique.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming skeleton catalyst in the prior art in catalytic hydrogenation
In the process, lighter hydrocarbons are mixed with hydrogen, cause hydrogen can not direct reuse the problem of, so that it is compound to provide a kind of copper-based skeleton
Membranous type hydrogenation catalyst, and further provide the preparation method and application of the compound membranous type hydrogenation catalyst of copper-based skeleton.
A kind of compound membranous type hydrogenation catalyst of copper-based skeleton, including catalyst body and the palladium for being coated on the body exterior
Film.
Preferably, in the compound membranous type hydrogenation catalyst of the copper-based skeleton, the content of palladium element accounts for the copper-based bone
The 1wt%-15wt% of the compound membranous type hydrogenation catalyst gross mass of frame.
Preferably, in the compound membranous type hydrogenation catalyst of the copper-based skeleton, the catalyst body is copper alloy, institute
Stating on catalyst body has several micropores.
It preferably, further include having in the catalyst body in the compound membranous type hydrogenation catalyst of the copper-based skeleton
Aluminium element and/or Zn-ef ficiency.
Preferably, in the compound membranous type hydrogenation catalyst of the copper-based skeleton, the content of copper accounts for the copper-based bone
The 70wt%-98wt% of the compound membranous type hydrogenation catalyst gross mass of frame.
Preferably, in the compound membranous type hydrogenation catalyst of the copper-based skeleton, the content of aluminium element and/or Zn-ef ficiency is accounted for
The 0.01wt%-25wt% of the compound membranous type hydrogenation catalyst gross mass of copper-based skeleton.
A method of the compound membranous type hydrogenation catalyst of copper-based skeleton is prepared, is included the following steps:
(1) catalyst body is prepared；
(2) palladium is coated on outside the catalyst body, forms palladium film, obtains the compound membranous type of copper-based skeleton and add hydrogen
Catalyst.
Preferably, in the preparation method, the preparation of the catalyst body includes:
Several metal powder is mixed, is melted, cold extraction obtains alloy presoma；
Alloy presoma is crushed, adhesive, extrusion forming is added, roasting obtains catalyst body presoma；
Using catalyst body presoma described in base extraction, washing to neutrality obtains that there is the described of several micropores to urge
Agent main body.
Preferably, in the preparation method, the specific steps of palladium film are formed are as follows:
Palladium salt solution, inorganic acid, ammonium hydroxide and ammonium chloride and sodium hypophosphite are mixed, adjust pH value later to 9-
10, obtain plating solution；
The catalyst body is placed in the plating solution, the institute for being coated with palladium is taken out in plating at being 40-60 DEG C in temperature
Catalyst body is stated, it is dry, obtain the compound membranous type hydrogenation catalyst of the copper-based skeleton.
One kind copper-based compound membranous type hydrogenation catalyst of skeleton of the present invention is in prepared by dimethyl oxalate plus hydrogen for glycolic
Application in methyl esters.
Technical solution of the present invention has the advantages that
1. the present invention provides a kind of copper-based compound membranous type hydrogenation catalyst of skeleton, in catalytic process, from catalytic bed
The hydrogen of outflow penetrates through palladium film by the palladium UF membrane being coated on outside catalyst, hydrogen, and then obtains from film side high-purity
The hydrogen of degree, so that hydrogen can be with direct reuse.Palladium film stops the reactants such as lighter hydrocarbons, esters and alcohols logical simultaneously
It crosses, these reactants flow out together with product from catalyst bed lower part, and reactor outlet has obtained oxalate and its hydrogen is added to produce
Object methyl glycollate.
2. having abandoned using silver, having been made with metallic copper the present invention provides a kind of copper-based compound membranous type hydrogenation catalyst of skeleton
For active component, the cost of catalyst is reduced.
3. adding hydrogen to urge in the compound membranous type of copper-based skeleton the present invention provides a kind of copper-based compound membranous type hydrogenation catalyst of skeleton
A high proportion of copper is used in agent, effectively raises the catalytic activity and selection of the compound membranous type hydrogenation catalyst of copper-based skeleton
Property, the generation of side reaction is reduced, the purity and yield of product are improved.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation method for present embodiments providing a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, includes the following steps:
(1) 12g aluminium powder, 15g copper powder and 1g zinc powder are mixed, stirs evenly, obtain mixed metal powder, by mixed metal
Powder is placed in high frequency furnace and melts, and cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 80-100 mesh particle, later with 5g polyvinyl alcohol, extrusion forming,
It is dry at being 120 DEG C in temperature, 1h is roasted at being later 900 DEG C in temperature, obtains catalyst body presoma；
(3) catalyst body precursor is placed in 10mL water, the sodium hydroxide solution of 15mL 50wt% is slowly added dropwise
It is 30min to the time used wherein, is added dropwise, constant temperature stirs 2h at 50 DEG C, takes out, and washing to neutrality is dry, is catalyzed
Agent main body；
(2) 50mL is contained to the palladium chloride of 10g/L, the stock solution of 36% (mL/L) hydrochloric acid is added drop-wise to 50mL ammonium chloride and hydrogen
In ammonium hydroxide solution, wherein the concentration of ammonium chloride is 3mol/L, and the concentration of ammonium hydroxide is 2mol/L, places for 24 hours, is then added
20g sodium hypophosphite adjusts pH value to 9.8 with sodium hydroxide, arrives plating solution；
(3) it to catalyst body surface degreasing, is placed in the nitric acid solution of 3wt% and activates, taking-up washing to neutrality, later
It is placed in plating solution, at 60 DEG C, plating 1h takes out and rinses drying, obtains the compound membranous type hydrogenation catalyst A of copper-based skeleton.
Wherein, in the compound membranous type hydrogenation catalyst A of copper-based skeleton, copper, aluminium, zinc and palladium account for copper-based skeleton composite membrane respectively
The 83% of type hydrogenation catalyst gross mass, 3%, 3%, 11%.
Embodiment 2
The preparation method for present embodiments providing a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, includes the following steps:
(1) 10g aluminium powder, 15g copper powder are mixed, stirs evenly, obtain mixed metal powder, mixed metal powder is placed in
It is melted in high frequency furnace, cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 20-60 mesh particle, later with 10g polyvinyl alcohol, extrusion forming,
It is dry at being 120 DEG C in temperature, 1h is roasted at being later 700 DEG C in temperature, obtains catalyst body presoma；
(3) catalyst body precursor is placed in 40mL water, the sodium hydroxide solution of 15mL 50wt% is slowly added dropwise
It is 30min to the time used wherein, is added dropwise, constant temperature stirs 2h at 50 DEG C, takes out, and washing to neutrality is dry, is catalyzed
Agent main body；
(2) 20mL is contained to the palladium chloride of 10g/L, the stock solution of 36% (mL/L) hydrochloric acid is added drop-wise to 50mL ammonium chloride and hydrogen
In ammonium hydroxide solution, wherein the concentration of ammonium chloride is 2mol/L, and the concentration of ammonium hydroxide is 1mol/L, places for 24 hours, is then added
10g sodium hypophosphite adjusts pH value to 9 with sodium hydroxide, obtains plating solution；
(3) it to catalyst body surface degreasing, is placed in the nitric acid solution of 3wt% and activates, taking-up washing to neutrality, later
It is placed in plating solution, at 50 DEG C, plating 1h takes out and rinses drying, obtains the compound membranous type hydrogenation catalyst B of copper-based skeleton.
Wherein, in the compound membranous type hydrogenation catalyst B of copper-based skeleton, copper, aluminium and palladium account for the compound membranous type of copper-based skeleton respectively
The 89% of hydrogenation catalyst gross mass, 1%, 10%.
Embodiment 3
The preparation method for present embodiments providing a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, includes the following steps:
(1) 5g aluminium powder, 20g copper powder and 1g zinc powder are mixed, stirs evenly, obtain mixed metal powder, by mixed metal
Powder is placed in high frequency furnace and melts, and cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 50-60 mesh particle, later with 6g polyvinyl alcohol, extrusion forming,
Temperature is drying at 110 DEG C, roasts 1h at being later 850 DEG C in temperature, obtains catalyst body presoma；
(3) catalyst body precursor is placed in 30mL water, the sodium hydroxide solution of 15mL 50wt% is slowly added dropwise
It is 30min to the time used wherein, is added dropwise, constant temperature stirs 2h at 50 DEG C, takes out, and washing to neutrality is dry, is catalyzed
Agent main body；
(2) 15mL is contained to the palladium chloride of 10g/L, the stock solution of 36% (mL/L) hydrochloric acid is added drop-wise to 30mL ammonium chloride and hydrogen
In ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.4mol/L, and the concentration of ammonium hydroxide is 0.2mol/L, is placed for 24 hours, then
10g sodium hypophosphite is added, adjusts pH value to 10 with sodium hydroxide, obtains plating solution；
(3) it to catalyst body surface degreasing, is placed in the nitric acid solution of 3wt% and activates, taking-up washing to neutrality, later
It is placed in plating solution, at 50 DEG C, plating 1h takes out and rinses drying, obtains the compound membranous type hydrogenation catalyst C of copper-based skeleton.
Wherein, in the compound membranous type hydrogenation catalyst C of copper-based skeleton, copper, aluminium, zinc and palladium account for copper-based skeleton composite membrane respectively
The 91% of type hydrogenation catalyst gross mass, 2%, 2%, 5%.
Embodiment 4
The preparation method for present embodiments providing a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, includes the following steps:
(1) 10g aluminium powder, 15g copper powder and 1g zinc powder are mixed, stirs evenly, obtain mixed metal powder, by mixed metal
Powder is placed in high frequency furnace and melts, and cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 50-60 mesh particle, later with 10g polyvinyl alcohol, extrusion forming,
It is dry at being 120 DEG C in temperature, 1h is roasted at being later 900 DEG C in temperature, obtains catalyst body presoma；
(3) catalyst body precursor is placed in 30mL water, the sodium hydroxide solution of 15mL 50wt% is slowly added dropwise
It is 30min to the time used wherein, is added dropwise, constant temperature stirs 2h at 50 DEG C, takes out, and washing to neutrality is dry, is catalyzed
Agent main body；
(2) 50mL is contained to the palladium chloride of 10g/L, the stock solution of 36% (mL/L) hydrochloric acid is added drop-wise to 40mL ammonium chloride and hydrogen
In ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.6mol/L, and the concentration of ammonium hydroxide is 0.3mol/L, is placed for 24 hours, then
15g sodium hypophosphite is added, adjusts pH value to 10 with sodium hydroxide, obtains plating solution；
(3) it to catalyst body surface degreasing, is placed in the nitric acid solution of 3wt% and activates, taking-up washing to neutrality, later
It is placed in plating solution, at 45 DEG C, plating 1h takes out and rinses drying, obtains the compound membranous type hydrogenation catalyst D of copper-based skeleton.
Wherein, in the compound membranous type hydrogenation catalyst D of copper-based skeleton, copper, aluminium, zinc and palladium account for copper-based skeleton composite membrane respectively
The 80% of type hydrogenation catalyst gross mass, 5%, 2%, 13%.
Embodiment 5
The preparation method for present embodiments providing a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, includes the following steps:
(1) 10g aluminium powder and 20g copper powder are mixed, stirs evenly, obtain mixed metal powder, mixed metal powder is set
It is melted in high frequency furnace, cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 50-60 mesh particle, later with 10g polyvinyl alcohol, extrusion forming,
It is dry at being 120 DEG C in temperature, 1h is roasted at being later 900 DEG C in temperature, obtains catalyst body presoma；
(3) catalyst body precursor is placed in 50mL water, the sodium hydroxide solution of 15mL 50wt% is slowly added dropwise
It is 30min to the time used wherein, is added dropwise, constant temperature stirs 2h at 50 DEG C, takes out, and washing to neutrality is dry, is catalyzed
Agent main body；
(2) 30mL is contained to the palladium chloride of 10g/L, the stock solution of 36% (mL/L) hydrochloric acid is added drop-wise to 50mL ammonium chloride and hydrogen
In ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.1mol/L, and the concentration of ammonium hydroxide is 0.2mol/L, is placed for 24 hours, then
5g sodium hypophosphite is added, adjusts pH value to 10 with sodium hydroxide, obtains plating solution；
(3) it to catalyst body surface degreasing, is placed in the nitric acid solution of 3wt% and activates, taking-up washing to neutrality, later
It is placed in plating solution, at 45 DEG C, plating 1h takes out and rinses drying, obtains the compound membranous type hydrogenation catalyst E of copper-based skeleton.
Wherein, in the compound membranous type hydrogenation catalyst E of copper-based skeleton, copper, aluminium and palladium account for the compound membranous type of copper-based skeleton respectively
The 70% of hydrogenation catalyst gross mass, 25%, 5%.
Comparative example
The preparation method for present embodiments providing a kind of hydrogenation catalyst, includes the following steps:
(1) 10g aluminium powder, 15g copper powder, 1g zinc powder and 2g palladium part are mixed, stirs evenly, obtains mixed metal powder, it will
Mixed metal powder is placed in high frequency furnace and melts, and cold extraction, obtains copper alloy later；
(2) by copper alloy powder be broken into mesh number be 50-60 mesh particle, later with 10g polyvinyl alcohol, extrusion forming,
It is dry at being 120 DEG C in temperature, 1h is roasted at being later 900 DEG C in temperature, obtains hydrogenation catalyst F；
Wherein, in the compound membranous type hydrogenation catalyst F of copper-based skeleton, copper, aluminium, zinc and palladium account for the total matter of hydrogenation catalyst respectively
The 83% of amount, 2%, 5%, 10%.
Compliance test result
Membranous type hydrogenation catalyst A-E's compound to the copper-based skeleton of the embodiment 1-5 and hydrogenation catalyst F of comparative example preparation urges
Change Hydrogenation to be tested, test result is shown in Table 1；
Specific test method are as follows:
Compound membranous type hydrogenation catalyst (or hydrogenation catalyst) 2mL of copper-based skeleton is filled in fixed-bed tube reactor
In, in air speed 3500h-1, pressure 0.5MPa H2350 DEG C are warming up to 2 DEG C/min under atmosphere, restores 8h at this temperature, it
The temperature of gas phase fixed bed is reduced to afterwards and reacts required temperature when occurring.Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate
Reaction condition is as follows: 250 DEG C of reaction temperature, reaction pressure 2.5MPa, liquid air speed is 1.9h-1, H2: mole of dimethyl oxalate
Than for 40:1.
Table 1
The selection %=(amount/theory for actually generating methyl glycollate generates the amount of methyl glycollate) of methyl glycollate ×
The selection %=(amount/theory for actually generating ethylene glycol generates the amount of ethylene glycol) × 100% of 100% ethylene glycol
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of compound membranous type hydrogenation catalyst of copper-based skeleton, which is characterized in that including catalyst body and be coated on the master
Palladium film outside body.
2. the compound membranous type hydrogenation catalyst of copper-based skeleton according to claim 1, which is characterized in that the content of palladium element accounts for
The 1wt%-15wt% of the compound membranous type hydrogenation catalyst gross mass of copper-based skeleton.
3. the compound membranous type hydrogenation catalyst of copper-based skeleton according to claim 1 or 2, which is characterized in that the catalyst
Main body is copper alloy, there is several micropores on the catalyst body.
4. the compound membranous type hydrogenation catalyst of copper-based skeleton according to claim 3, which is characterized in that the catalyst body
In further include having aluminium element and/or Zn-ef ficiency.
5. the compound membranous type hydrogenation catalyst of copper-based skeleton according to claim 5, which is characterized in that the content of copper accounts for
The 70wt%-98wt% of the compound membranous type hydrogenation catalyst gross mass of copper-based skeleton.
6. the compound membranous type hydrogenation catalyst of copper-based skeleton according to claim 4 or 5, which is characterized in that aluminium element and/or
The content of Zn-ef ficiency accounts for the 0.01wt%-25wt% of the compound membranous type hydrogenation catalyst gross mass of the copper-based skeleton.
7. a kind of method for preparing any compound membranous type hydrogenation catalyst of copper-based skeleton of claim 1-6, including it is as follows
Step:
(1) catalyst body is prepared；
(2) palladium is coated on outside the catalyst body, forms palladium film, obtains the compound membranous type hydrogenation catalyst of the copper-based skeleton
Agent.
8. preparation method according to claim 7, which is characterized in that the preparation of the catalyst body includes:
Several metal powder is mixed, is melted, cold extraction obtains alloy presoma；
Alloy presoma is crushed, adhesive, extrusion forming is added, roasting obtains catalyst body presoma；
Using catalyst body presoma described in base extraction, washs to neutrality, obtain the catalyst with several micropores
Main body.
9. preparation method according to claim 7 or 8, which is characterized in that form the specific steps of palladium film are as follows:
Palladium salt solution, inorganic acid, ammonium hydroxide and ammonium chloride and sodium hypophosphite are mixed, pH value is adjusted later to 9-10, obtains
To plating solution；
The catalyst body is placed in the plating solution, plating at being 40-60 DEG C in temperature, taking-up is coated with the described of palladium and urges
Agent main body, it is dry, obtain the compound membranous type hydrogenation catalyst of the copper-based skeleton.
10. a kind of claim 1-6 any compound membranous type hydrogenation catalyst of copper-based skeleton or any system of claim 7-9
The compound membranous type hydrogenation catalyst of standby copper-based skeleton is in prepared by dimethyl oxalate plus hydrogen for the application in methyl glycollate.
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