CN109954500B - Copper-based skeleton composite membrane type hydrogenation catalyst, and preparation method and application thereof - Google Patents
Copper-based skeleton composite membrane type hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a copper-based framework composite membrane type hydrogenation catalyst, wherein hydrogen flowing out of a catalytic bed layer is separated by virtue of a palladium membrane coated outside the catalyst in the catalytic process, and the hydrogen permeates through the palladium membrane, so that high-purity hydrogen is obtained from the membrane side, and the hydrogen can be directly recycled. The palladium membrane simultaneously blocks the reactants such as light hydrocarbon, esters, alcohols and the like from passing through, the reactants and products flow out from the lower part of the catalyst bed layer, and oxalic ester and hydrogenation products methyl glycolate thereof are obtained at the outlet of the reactor.
Description
Technical Field
The invention relates to the technical field of catalysts, and belongs to a hydrogenation catalyst for preparing methyl glycolate through dimethyl oxalate hydrogenation.
Background
Methyl glycolate is colorless transparent liquid, and has molecular formula of C 3 H 6 O 3 Is an important chemical intermediate and solvent, and is widely applied to the technical fields of chemical industry, pesticides, medicines, dyes and the like. The most commonly used preparation processes of methyl glycolate at present are formaldehyde and formaldehyde free radical addition method, chloroacetic acid method and dimethyl oxalate hydrogenation method.
The formaldehyde and formaldehyde free radical addition method is that formaldehyde and methylal generate methyl glycolate under the action of a peroxide catalyst, the production process flow is simple and easy to operate, but the peroxidation has higher corrosivity, so the corrosion resistance requirement on a reacted instrument is high, and the side reaction is more in the production process, so that the content of the prepared methyl glycolate is lower.
Chloroacetic acid method is to mix chloroacetic acid with caustic soda to generate glycolic acid, then to react glycolic acid with methanol and concentrated sulfuric acid to generate methyl glycolate, and the chloroacetic acid method is to obtain methyl glycolate, although the yield is high, pollution is serious in the preparation process, the wastewater treatment difficulty in the process generation is high, and the product methyl glycolate is also often accompanied with chloride ions, so that separation is also difficult.
The dimethyl oxalate hydrogenation method is that dimethyl oxalate reacts with high-pressure hydrogen under the action of a catalyst to generate methyl glycolate, and the production process has little pollution and high yield, and is the most green and environment-friendly process for producing methyl glycolate at present. In the dimethyl oxalate hydrogenation process, the catalyst plays a critical role, and directly influences the yield and purity of methyl glycolate. Conventional catalysts use silver catalysts, but the commercial use of silver is limited due to its high price.
The skeleton catalyst is also called Raney catalyst, and is a hydrogenation catalyst with higher catalytic activity. The skeleton catalyst is formed by forming a bulk alloy by catalytic metal and aluminum or silicon, and then leaching the aluminum and the silicon by sodium hydroxide to form the skeleton catalyst with larger specific surface area and catalytic activity.
Since the skeletal catalyst has the above-mentioned advantages, it is used in the dimethyl oxalate hydrogenation process. For example, chinese patent document CN101254466a discloses a method for preparing a supported raney catalyst, which discloses externally covering aluminum, an aluminum alloy or a mixture of aluminum with a metal capable of forming a raney skeleton catalyst, melting aluminum at a high temperature, but keeping the metal of the raney skeleton catalyst unmelted, cold extracting, treating with sodium hydroxide to obtain a supported raney catalyst, and discloses that the metal capable of forming a raney skeleton catalyst is nickel, copper, iron, chromium, silver or platinum, and the aluminum alloy is formed of aluminum with nickel, copper, cobalt, iron or platinum, etc. The catalyst has better hydrogenation catalytic activity and long catalytic life. However, the gas phase product generated in the catalytic process of the supported Raney catalyst disclosed in the patent document, such as low molecular weight light hydrocarbon, can be mixed with hydrogen, so that the partial pressure of hydrogen in a circulation loop is reduced, the hydrogenation efficiency is affected, meanwhile, the hydrogen released in the hydrogenation process cannot be recycled, a separation device is additionally arranged, the catalyst can be used after being treated, and the process cost is increased.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problem that the hydrogen cannot be directly recycled due to the mixing of light hydrocarbon and hydrogen in the catalytic hydrogenation process of the framework catalyst in the prior art, thereby providing the copper-based framework composite membrane type hydrogenation catalyst, and further providing the preparation method and the application of the copper-based framework composite membrane type hydrogenation catalyst.
A copper-based skeleton composite membrane type hydrogenation catalyst comprises a catalyst main body and a palladium membrane coated outside the main body.
Preferably, in the copper-based skeleton composite membrane type hydrogenation catalyst, the content of palladium element accounts for 1-15 wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Preferably, in the copper-based skeleton composite membrane type hydrogenation catalyst, the catalyst main body is made of copper alloy, and a plurality of micropores are formed in the catalyst main body.
Preferably, in the copper-based skeleton composite membrane type hydrogenation catalyst, the catalyst main body further comprises aluminum element and/or zinc element.
Preferably, in the copper-based skeleton composite membrane type hydrogenation catalyst, the content of copper element accounts for 70-98 wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Preferably, in the copper-based skeleton composite membrane type hydrogenation catalyst, the content of aluminum element and/or zinc element accounts for 0.01wt% to 25wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
A method for preparing a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Preparing a catalyst body;
(2) And coating palladium on the outside of the catalyst main body to form a palladium membrane, thereby obtaining the copper-based skeleton composite membrane type hydrogenation catalyst.
Preferably, in the preparation method, the preparation of the catalyst body includes:
mixing, melting and cold extracting a plurality of metal powders to obtain an alloy precursor;
crushing the alloy precursor, adding an adhesive, extruding, forming and roasting to obtain a catalyst main body precursor;
and (3) treating the catalyst main body precursor by adopting alkali liquor, and washing to neutrality to obtain the catalyst main body with a plurality of micropores.
Preferably, in the preparation method, the specific steps of forming the palladium membrane are as follows:
mixing palladium salt solution, inorganic acid, ammonium hydroxide, ammonium chloride and sodium hypophosphite, and then regulating the pH value to 9-10 to obtain plating solution;
and placing the catalyst main body in the plating solution, plating at the temperature of 40-60 ℃, taking out the catalyst main body coated with palladium, and drying to obtain the copper-based skeleton composite membrane type hydrogenation catalyst.
The invention discloses an application of a copper-based skeleton composite membrane type hydrogenation catalyst in preparing methyl glycolate through dimethyl oxalate hydrogenation.
The technical scheme of the invention has the following advantages:
1. the invention provides a copper-based framework composite membrane type hydrogenation catalyst, wherein hydrogen flowing out of a catalytic bed layer is separated by virtue of a palladium membrane coated outside the catalyst in the catalytic process, and the hydrogen permeates through the palladium membrane, so that high-purity hydrogen is obtained from the membrane side, and the hydrogen can be directly recycled. The palladium membrane simultaneously blocks the reactants such as light hydrocarbon, esters, alcohols and the like from passing through, the reactants and products flow out from the lower part of the catalyst bed layer, and oxalic ester and hydrogenation products methyl glycolate thereof are obtained at the outlet of the reactor.
2. The invention provides a copper-based skeleton composite membrane type hydrogenation catalyst, which eliminates the use of silver and takes metallic copper as an active component, thereby reducing the cost of the catalyst.
3. The invention provides a copper-based framework composite membrane type hydrogenation catalyst, which uses high proportion of copper in the copper-based framework composite membrane type hydrogenation catalyst, effectively improves the catalytic activity and selectivity of the copper-based framework composite membrane type hydrogenation catalyst, reduces the generation of side reaction, and improves the purity and yield of the product.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Mixing 12g of aluminum powder, 15g of copper powder and 1g of zinc powder, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 80-100, mixing with 5g of polyvinyl alcohol, extruding for molding, drying at the temperature of 120 ℃, and roasting at the temperature of 900 ℃ for 1h to obtain a catalyst main body precursor;
(3) Putting a catalyst main body precursor into 10mL of water, slowly dropwise adding 15mL of 50wt% sodium hydroxide solution into the water for 30min, stirring the mixture at a constant temperature of 50 ℃ for 2h, taking out the mixture, washing the mixture to be neutral, and drying the mixture to obtain a catalyst main body;
(2) 50mL of a stock solution containing 10g/L of palladium chloride and 36% (mL/L) of hydrochloric acid is dripped into 50mL of ammonium chloride and ammonium hydroxide solution, wherein the concentration of the ammonium chloride is 3mol/L, the concentration of the ammonium hydroxide is 2mol/L, the solution is left for 24 hours, then 20g of sodium hypophosphite is added, and the pH value is regulated to 9.8 by sodium hydroxide to the plating solution;
(3) Deoiling the surface of the catalyst main body, placing the catalyst main body into a nitric acid solution with the concentration of 3wt percent for activation, taking out and washing the catalyst main body to be neutral, then placing the catalyst main body into a plating solution, plating the catalyst main body for 1h at the temperature of 60 ℃, taking out, washing and drying the catalyst main body, and obtaining the copper-based skeleton composite membrane type hydrogenation catalyst A.
Wherein, in the copper-based skeleton composite membrane type hydrogenation catalyst A, copper, aluminum, zinc and palladium respectively account for 83%,3%,3% and 11% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Example 2
The embodiment provides a preparation method of a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Mixing 10g of aluminum powder and 15g of copper powder, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 20-60, mixing with 10g of polyvinyl alcohol, extruding for molding, drying at the temperature of 120 ℃, and roasting at the temperature of 700 ℃ for 1h to obtain a catalyst main body precursor;
(3) Putting a catalyst main body precursor into 40mL of water, slowly dropwise adding 15mL of 50wt% sodium hydroxide solution into the water for 30min, stirring the mixture at a constant temperature of 50 ℃ for 2h, taking out the mixture, washing the mixture to be neutral, and drying the mixture to obtain a catalyst main body;
(2) Dropwise adding 20mL of a stock solution containing 10g/L of palladium chloride and 36% (mL/L) of hydrochloric acid into 50mL of ammonium chloride and ammonium hydroxide solution, wherein the concentration of the ammonium chloride is 2mol/L, the concentration of the ammonium hydroxide is 1mol/L, standing for 24 hours, adding 10g of sodium hypophosphite, and regulating the pH value to 9 by using sodium hydroxide to obtain a plating solution;
(3) Deoiling the surface of the catalyst main body, placing the catalyst main body into a nitric acid solution with the concentration of 3wt percent for activation, taking out and washing the catalyst main body to be neutral, then placing the catalyst main body into a plating solution, plating the catalyst main body for 1h at 50 ℃, taking out, washing and drying the catalyst main body, and obtaining the copper-based skeleton composite membrane type hydrogenation catalyst B.
Wherein, in the copper-based skeleton composite membrane type hydrogenation catalyst B, copper, aluminum and palladium respectively account for 89 percent, 1 percent and 10 percent of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Example 3
The embodiment provides a preparation method of a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Mixing 5g of aluminum powder, 20g of copper powder and 1g of zinc powder, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 50-60, mixing with 6g of polyvinyl alcohol, extruding for molding, drying at the temperature of 110 ℃, and roasting at the temperature of 850 ℃ for 1h to obtain a catalyst main body precursor;
(3) Putting a catalyst main body precursor into 30mL of water, slowly dropwise adding 15mL of 50wt% sodium hydroxide solution into the water for 30min, stirring the mixture at a constant temperature of 50 ℃ for 2h, taking out the mixture, washing the mixture to be neutral, and drying the mixture to obtain a catalyst main body;
(2) 15mL of stock solution containing 10g/L of palladium chloride and 36% (mL/L) of hydrochloric acid is dripped into 30mL of ammonium chloride and ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.4mol/L, the concentration of ammonium hydroxide is 0.2mol/L, the solution is left for 24 hours, then 10g of sodium hypophosphite is added, and the pH value is regulated to 10 by sodium hydroxide, so that plating solution is obtained;
(3) Deoiling the surface of the catalyst main body, placing the catalyst main body into a nitric acid solution with the concentration of 3wt percent for activation, taking out and washing the catalyst main body to be neutral, then placing the catalyst main body into a plating solution, plating the catalyst main body for 1h at 50 ℃, taking out, washing and drying the catalyst main body, and obtaining the copper-based skeleton composite membrane type hydrogenation catalyst C.
Wherein, in the copper-based skeleton composite membrane type hydrogenation catalyst C, copper, aluminum, zinc and palladium respectively account for 91 percent, 2 percent and 5 percent of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Example 4
The embodiment provides a preparation method of a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Mixing 10g of aluminum powder, 15g of copper powder and 1g of zinc powder, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 50-60, mixing with 10g of polyvinyl alcohol, extruding for molding, drying at the temperature of 120 ℃, and roasting at the temperature of 900 ℃ for 1h to obtain a catalyst main body precursor;
(3) Putting a catalyst main body precursor into 30mL of water, slowly dropwise adding 15mL of 50wt% sodium hydroxide solution into the water for 30min, stirring the mixture at a constant temperature of 50 ℃ for 2h, taking out the mixture, washing the mixture to be neutral, and drying the mixture to obtain a catalyst main body;
(2) 50mL of stock solution containing 10g/L of palladium chloride and 36% (mL/L) of hydrochloric acid is dripped into 40mL of ammonium chloride and ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.6mol/L, the concentration of ammonium hydroxide is 0.3mol/L, the solution is left for 24 hours, then 15g of sodium hypophosphite is added, and the pH value is regulated to 10 by sodium hydroxide, so that plating solution is obtained;
(3) Deoiling the surface of the catalyst main body, placing the catalyst main body into a nitric acid solution with the concentration of 3wt percent for activation, taking out and washing the catalyst main body to be neutral, then placing the catalyst main body into a plating solution, plating the catalyst main body for 1h at the temperature of 45 ℃, taking out, washing and drying the catalyst main body, and obtaining the copper-based skeleton composite membrane type hydrogenation catalyst D.
Wherein, in the copper-based skeleton composite membrane type hydrogenation catalyst D, copper, aluminum, zinc and palladium respectively account for 80%,5%,2% and 13% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Example 5
The embodiment provides a preparation method of a copper-based framework composite membrane type hydrogenation catalyst, which comprises the following steps:
(1) Mixing 10g of aluminum powder and 20g of copper powder, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 50-60, mixing with 10g of polyvinyl alcohol, extruding for molding, drying at the temperature of 120 ℃, and roasting at the temperature of 900 ℃ for 1h to obtain a catalyst main body precursor;
(3) Putting a catalyst main body precursor into 50mL of water, slowly dropwise adding 15mL of 50wt% sodium hydroxide solution into the water for 30min, stirring the mixture at a constant temperature of 50 ℃ for 2h, taking out the mixture, washing the mixture to be neutral, and drying the mixture to obtain a catalyst main body;
(2) Dropwise adding 30mL of a stock solution containing 10g/L of palladium chloride and 36% (mL/L) of hydrochloric acid into 50mL of ammonium chloride and ammonium hydroxide solution, wherein the concentration of ammonium chloride is 0.1mol/L, the concentration of ammonium hydroxide is 0.2mol/L, standing for 24 hours, adding 5g of sodium hypophosphite, and regulating the pH value to 10 by using sodium hydroxide to obtain a plating solution;
(3) Deoiling the surface of the catalyst main body, placing the catalyst main body into a nitric acid solution with the concentration of 3wt percent for activation, taking out and washing the catalyst main body to be neutral, then placing the catalyst main body into a plating solution, plating the catalyst main body for 1h at the temperature of 45 ℃, taking out, washing and drying the catalyst main body, and obtaining the copper-based skeleton composite membrane type hydrogenation catalyst E.
Wherein, in the copper-based skeleton composite membrane type hydrogenation catalyst E, copper, aluminum and palladium respectively account for 70%,25% and 5% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
Comparative example
The embodiment provides a preparation method of a hydrogenation catalyst, which comprises the following steps:
(1) Mixing 10g of aluminum powder, 15g of copper powder, 1g of zinc powder and 2g of palladium, uniformly stirring to obtain mixed metal powder, melting the mixed metal powder in a high-frequency electric furnace, and then carrying out cold extraction to obtain copper alloy;
(2) Crushing copper alloy into particles with the mesh number of 50-60, mixing with 10g of polyvinyl alcohol, extruding for molding, drying at the temperature of 120 ℃, and roasting at the temperature of 900 ℃ for 1h to obtain a hydrogenation catalyst F;
in the copper-based skeleton composite membrane type hydrogenation catalyst F, copper, aluminum, zinc and palladium respectively account for 83%,2%,5% and 10% of the total mass of the hydrogenation catalyst.
Effect verification
The catalytic hydrogenation performance of the copper-based skeleton composite membrane type hydrogenation catalysts A-E of examples 1-5 and the hydrogenation catalyst F prepared in comparative example were tested, and the test results are shown in Table 1;
the specific test method comprises the following steps:
2mL of copper-based framework composite membrane type hydrogenation catalyst (or hydrogenation catalyst) is filled in a fixed bed tubular reactor, and the space velocity is 3500h -1 H at a pressure of 0.5MPa 2 The temperature was raised to 350 ℃ at 2 ℃/min under an atmosphere, reduced at this temperature for 8 hours, after which the temperature of the gas-phase fixed bed was reduced to the temperature required for the reaction to take place. The reaction conditions for synthesizing methyl glycolate through hydrogenation of dimethyl oxalate are as follows: the reaction temperature is 250 ℃, the reaction pressure is 2.5MPa, and the liquid space velocity is 1.9h -1 ，H 2 : the molar ratio of the dimethyl oxalate is 40:1.
TABLE 1
Methyl glycolate = (amount of actual produced methyl glycolate/amount of theoretical produced methyl glycolate) ×100% of ethylene glycol = (amount of actual produced ethylene glycol/amount of theoretical produced ethylene glycol) ×100% of ethylene glycol
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. The copper-based skeleton composite membrane type hydrogenation catalyst is characterized by comprising a catalyst main body and a palladium membrane coated outside the main body;
the content of palladium element accounts for 1-15 wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst;
the catalyst main body is made of copper alloy, and a plurality of micropores are formed in the catalyst main body;
the catalyst main body also comprises aluminum element and/or zinc element;
the palladium membrane is used for separating hydrogen;
the preparation method of the hydrogenation catalyst comprises the following steps:
(1) Preparing a catalyst body;
(2) Coating palladium on the outside of the catalyst main body to form a palladium membrane, thereby obtaining the copper-based skeleton composite membrane type hydrogenation catalyst;
the preparation of the catalyst body comprises:
mixing, melting and cold extracting a plurality of metal powders to obtain an alloy precursor;
crushing the alloy precursor, adding an adhesive, extruding, forming and roasting to obtain a catalyst main body precursor;
treating the catalyst main body precursor by adopting alkali liquor, and washing to neutrality to obtain the catalyst main body with a plurality of micropores;
the specific steps for forming the palladium membrane are as follows:
mixing palladium salt solution, inorganic acid, ammonium hydroxide, ammonium chloride and sodium hypophosphite, and then regulating the pH value to 9-10 to obtain plating solution;
and placing the catalyst main body in the plating solution, plating at the temperature of 40-60 ℃, taking out the catalyst main body coated with palladium, and drying to obtain the copper-based skeleton composite membrane type hydrogenation catalyst.
2. The copper-based skeleton composite membrane type hydrogenation catalyst according to claim 1, wherein the content of copper element is 70-98 wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
3. The copper-based skeleton composite membrane type hydrogenation catalyst according to claim 1 or 2, wherein the content of aluminum element and/or zinc element is 0.01wt% to 25wt% of the total mass of the copper-based skeleton composite membrane type hydrogenation catalyst.
4. A method of preparing the copper-based skeletal composite membrane hydrogenation catalyst of any one of claims 1 to 3, comprising the steps of:
(1) Preparing a catalyst body;
(2) Coating palladium on the outside of the catalyst main body to form a palladium membrane, thereby obtaining the copper-based skeleton composite membrane type hydrogenation catalyst;
the preparation of the catalyst body comprises:
mixing, melting and cold extracting a plurality of metal powders to obtain an alloy precursor;
crushing the alloy precursor, adding an adhesive, extruding, forming and roasting to obtain a catalyst main body precursor;
treating the catalyst main body precursor by adopting alkali liquor, and washing to neutrality to obtain the catalyst main body with a plurality of micropores;
the specific steps for forming the palladium membrane are as follows:
mixing palladium salt solution, inorganic acid, ammonium hydroxide, ammonium chloride and sodium hypophosphite, and then regulating the pH value to 9-10 to obtain plating solution;
and placing the catalyst main body in the plating solution, plating at the temperature of 40-60 ℃, taking out the catalyst main body coated with palladium, and drying to obtain the copper-based skeleton composite membrane type hydrogenation catalyst.
5. Use of the copper-based skeleton composite membrane type hydrogenation catalyst of any one of claims 1 to 3 or the copper-based skeleton composite membrane type hydrogenation catalyst prepared by the method of claim 4 in preparing methyl glycolate through dimethyl oxalate hydrogenation.
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