CN107952450B - Preparation method of silver-carbonized raney copper catalyst, catalyst and application - Google Patents

Preparation method of silver-carbonized raney copper catalyst, catalyst and application Download PDF

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CN107952450B
CN107952450B CN201610899111.XA CN201610899111A CN107952450B CN 107952450 B CN107952450 B CN 107952450B CN 201610899111 A CN201610899111 A CN 201610899111A CN 107952450 B CN107952450 B CN 107952450B
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silver
catalyst
solution
raney copper
raney
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CN107952450A (en
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彭晖
吴佳佳
鲁树亮
张晓红
王秀玲
蒋海斌
乐毅
刘海江
汪晓菁
郝雪松
徐洋
乔金樑
戴伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • B01J25/00—Catalysts of the Raney type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond

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Abstract

The invention discloses a preparation method of a silver-carbonized raney copper catalyst, the catalyst and application. The method comprises the following steps: (1) uniformly mixing the Raney alloy particles with a curing system of a carbonizable organic substance, and then curing to obtain a catalyst precursor; (2) carbonizing the obtained catalyst precursor at high temperature under the protection of inert gas, and activating to obtain a carbonized raney copper catalyst; (3) preparing a mixed solution of soluble organic amine and water, and dissolving soluble silver salt and soluble salts of other assistants to prepare a silver source solution; (4) and (3) adding a Raney copper carbide catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (3) into the Raney copper carbide catalyst solution, reacting and washing to obtain the silver Raney copper carbide catalyst. The catalyst can remove alkyne in the liquid-phase carbon four-fraction to below 30ppm, and the loss rate of 1, 3-butadiene is controlled to below 3%.

Description

Preparation method of silver-carbonized raney copper catalyst, catalyst and application
Technical Field
The invention relates to the field of a carbon four selective hydrogenation acetylene removal catalyst, and further relates to a preparation method of a silver-carbonized raney copper catalyst, the catalyst and application.
Background
The 1, 3-butadiene is an important chemical raw material for producing synthetic rubber, and the cracking mixed carbon C contains about 40-50% of the 1, 3-butadiene, which is a main source of the butadiene. The requirement of polymerization grade diene on alkyne impurities is high, for example, the purity of polymerization grade butadiene is required to be more than 99.7%, and the alkyne content is less than 50 ppm. In order to meet the requirements of the polymerization grade, the alkyne removal treatment needs to be carried out on the carbon four-cut fraction. At present, the industrially adopted process for separating butadiene from mixed C4 mainly adopts a two-stage solvent extraction rectification process, wherein one stage is used for separating butene, butane and the like from crude butadiene, and the other stage is used for removing alkynes (comprising Vinyl Acetylene (VA), ethyl acetylene (MA) and Methyl Acetylene (MA)) in the crude butadiene, and then the polymerization-grade butadiene can be obtained through rectification purification.
The selective hydrogenation for removing the alkyne in the carbon four fraction is a more economical alkyne removal method. The method utilizes a selective hydrogenation catalyst to convert alkynes such as methylacetylene, ethylacetylene, vinylacetylene and the like in the carbon four-fraction into butadiene, butene and a small amount of butane through hydrogenation reaction, and not only can effectively remove the alkynes, but also can simplify the butadiene separation process. The alkyne removing method not only requires that alkyne can be effectively removed, but also reduces the loss of 1, 3-butadiene as much as possible, so that the requirement on the selectivity of the catalyst is very high; in addition, high stability is also important for long-term, low-cost operation.
The copper-based catalyst has high selectivity for selective hydrogenation and acetylene removal, and the patent US4440956 indicates that the copper-based catalyst is used for selective hydrogenation and acetylene removal of carbon four under the premise of removing indexes, the loss of butadiene is low, the selectivity is good, but the space velocity is low, the service life is short, and frequent regeneration is required.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a silver-carbonized raney copper catalyst, the catalyst and application. The catalyst can be used for the reaction at the reaction inlet temperature of 30-60 ℃, the reaction pressure of 0.5-2.0 MPa and the reaction space velocity measured by the liquid volume of the carbon four-fraction of 2-20 h-1And under the condition that the volume ratio of hydrogen to alkyne is 0.2-10 mol/mol, removing alkyne in the liquid phase carbon four-fraction to be below 30ppm, and controlling the loss rate of 1, 3-butadiene to be below 3%.
One of the purposes of the invention is to provide a preparation method of a silver-carbonized raney copper catalyst.
The method comprises the following steps:
(1) uniformly mixing the Raney alloy particles with a curing system of a carbonizable organic substance, and then curing to obtain a catalyst precursor; the weight ratio of the Raney alloy particles to the organic matter curing system capable of being carbonized is 1: 99-99: 1; preferably 10: 90-90: 10; more preferably 25: 75-75: 25;
the curing system of the carbonizable organic matter comprises the carbonizable organic matter and additives;
(2) carbonizing the obtained catalyst precursor at high temperature under the protection of inert gas, and activating to obtain a carbonized raney copper catalyst;
the particle size of the carbonized raney copper catalyst particles is 2-3 mm.
The conventional preparation method of the raney copper catalyst can be adopted, and in the invention, the following steps can be preferably carried out: the caustic alkali is preferably NaOH, the concentration of the caustic alkali aqueous solution is 2-40 wt%, preferably 5-20 wt%, the extraction temperature is 20-100 ℃, the extraction time is 0.5-3 h, and the dosage of the caustic alkali is 1-3 times, preferably 1-2 times of the mass of the alloy.
(3) Preparing a mixed solution of soluble organic amine and water, and dissolving soluble silver salt and soluble salts of other assistants to prepare a silver source solution;
the molar ratio of the organic amine to the silver salt solution is 1: 1-10: 1; preferably, the ratio of 2: 1-5: 1;
the mol ratio of the organic amine to the auxiliary agent is 1: 2-10: 1 of the total amount of the active ingredients,
other auxiliary agents comprise one or more of Co, Fe, Mn, Ni, Zn, Cr and Pd;
the soluble organic amine is one or more of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, isopropylamine, diethylamine, aniline, N-dimethylaniline, dodecylamine, triethylenediamine, cyclohexylamine and hexamethylenetetramine; preferably one or more of triethanolamine, ethanolamine, ethylenediamine and hexamethylenediamine;
(4) adding a Raney copper carbide catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (3) into the Raney copper carbide catalyst solution, reacting for 1-2 hours, and washing to obtain a silver Raney copper carbide catalyst;
the mass of the silver in the silver source solution is 0.01 w-1.0 wt% of that of the Raney copper carbide catalyst; preferably 0.1 wt% to 0.6 wt%;
the mass of the auxiliary metal in the silver source solution is 0-5 wt% of the Raney copper carbide catalyst, preferably 0.1-1.0 wt%;
the carbonizable organic substance means: treating organic matters at a certain temperature and under a certain atmosphere condition, and volatilizing all or part of hydrogen, oxygen, nitrogen, sulfur and the like in the organic matters, thereby obtaining a synthetic material with high carbon content, wherein the obtained carbon material has the properties of high temperature resistance, high strength, high modulus, porosity and the like; the organic matter capable of being carbonized is an organic high molecular compound;
the organic polymer compound that can be carbonized is preferably: at least one of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, starch, viscose, lignin, cellulose, styrene-butadiene rubber and polyurethane rubber;
the Raney alloy particles are distributed in the gaps of the carbon, and the porous carbon structure effectively disperses the Raney alloy particles, so that the sintering of the Raney alloy particles is reduced as much as possible in the high-temperature reaction process, and the service life of the catalyst is effectively prolonged. In addition, the solution or gas can easily contact with the Raney alloy, the composite catalyst is soaked by alkali liquor, the Raney alloy particles are activated to form porous high-activity Raney metal, a small amount of amorphous carbon is washed away, the continuous-phase carbon material is expanded, more Raney alloy is exposed, and therefore the catalyst has high activity.
The additives may be those commonly used in the art, such as: curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblocking agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, or combinations thereof. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions.
Wherein,
the carbonization temperature in the step (2) is 400-1200 ℃; preferably 600-950 ℃, the protective gas is inert gas such as nitrogen or argon, and the like, and the carbonization is carried out for 1-6 hours.
In the step (3), the soluble salt of silver is nitrate, and the other auxiliary agent soluble salt is nitrate, chloride or acetate.
Raney alloys include metallic copper and metallic aluminum.
The second purpose of the invention is to provide a silver-carbonized Raney copper catalyst prepared by the method.
The invention also aims to provide the application of the silver-carbonized Raney copper catalyst prepared by the method in the removal of alkyne by carbon tetrahydrogen.
The reaction inlet temperature is 30-60 ℃, the reaction pressure is 0.5-2.0 MPa, and the reaction space velocity measured by the liquid volume of the carbon four-fraction is 2-20 h-1Removing alkyne in the liquid phase carbon four-fraction to below 30ppm under the condition that the volume ratio of hydrogen to alkyne is 0.2-10 mol/mol, and controlling the loss rate of 1, 3-butadiene to below 3%
The preparation method of the invention adopts the technical scheme that:
(1) the composite catalyst is prepared by the following steps:
a. preparing a curing system according to a common curing formula of the organic matter capable of being carbonized, wherein the curing system is in a liquid state or a powder state;
b. uniformly mixing the Raney alloy particles with a curing system of a carbonizable organic substance, and then curing to obtain a catalyst precursor;
c. under the protection of inert gas, carbonizing the obtained catalyst precursor at high temperature to obtain a catalyst, and then activating to obtain the carbonized raney copper catalyst.
(2) Preparing a mixed solution of soluble organic amine and water, dissolving soluble silver salt and soluble salts of other assistants, wherein the other assistants comprise one or more of Co, Fe, Mn, Ni, Zn, Cr and Pd, and preparing the silver source solution.
(3) And (3) adding a Raney's copper carbide catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (2) into the Raney's copper carbide catalyst solution, reacting for 1-2 hours without adjusting the pH value and any reducing agent, taking out the catalyst, and washing the catalyst with deionized water for three times for later use.
Preferably:
in the step (1), the organic matter capable of being carbonized is: treating organic matter at certain temperature and atmosphere condition to volatilize all or part of hydrogen, oxygen, nitrogen, sulfur, etc. in the organic matter to obtain one kind of synthetic material with high carbon content.
In step a, the curing system is prepared according to a common curing formula of the carbonizable organic matter, and one or more optional additives selected from the following additives can be added during preparation: cure accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblock agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, and the like. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions. The prepared solidification system is a liquid system or a powder system, and the liquid system can be directly stirred uniformly; the powdery solid system can be directly and uniformly blended; the granular solid system can be pulverized by any pulverizing equipment commonly used in industry and then uniformly blended.
In step b, the weight ratio of the raney alloy particles to the carbonizable organic curing system is 1: 99-99: 1, preferably 10: 90-90: 10, more preferably 25: 75-75: 25. the obtained catalyst precursor can be processed into particles which can be used in a fixed bed or a fluidized bed reaction by cutting, stamping or crushing and the like by adopting any available organic polymer material processing equipment, the particle size of the particles is based on the particle size which can meet the requirement of a fixed bed catalyst or a fluidized bed catalyst, and the shape of the particles can be any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, tooth shape or the combination of the shapes, and the like, preferably spherical, annular, tooth shape, cylindrical or the combination of the shapes.
And c, carbonizing in the step c generally in a tubular heating furnace, wherein the carbonizing operation temperature is generally 400-1900 ℃, preferably 600-950 ℃, and the protective gas is inert gas such as nitrogen or argon, and carbonizing for 1-12 hours. For example, phenolic resin is carbonized at 850 ℃ for 3 hours, and then the phenolic resin is completely carbonized to form porous carbon. The higher carbonization temperature can make the carbon obtained after carbonization more regular.
In the activation process in the step c, the particle size of the Raney copper carbide catalyst is not limited by a fixed mesh number, and the preferred particle size is 2-3 mm. The caustic alkali is preferably NaOH, the concentration of the caustic alkali aqueous solution is 2-40 wt%, preferably 5-20 wt%, the extraction temperature is 20-100 ℃, the extraction time is 0.5-3 h, and the dosage of the caustic alkali is 1-3 times, preferably 1-2 times of the mass of the alloy. Preferably, the extracted Raney copper catalyst is washed by deionized water at the temperature of 20-50 ℃ until the pH value of the washing liquid is 7-9, and the finally obtained catalyst is stored in the deionized water or absolute ethyl alcohol.
In the step (2), the soluble salt of silver is nitrate, and the mass of silver in the silver source solution is 0.05-2.0 wt% of the mass of the catalyst added with the Raney copper carbide. The other auxiliary agent soluble salt is nitrate, chloride or acetate, and the total content of the other auxiliary agent soluble salt is 0-5%, preferably 0.1-2.0%. The soluble organic amine is one or more of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, isopropylamine, aniline, N-dimethylaniline, dodecylamine, triethylene diamine, cyclohexylamine and hexamethylenetetramine, and preferably one or more of triethanolamine, ethanolamine, ethylenediamine and hexamethylenediamine.
In the step (3), the silver-carbonized raney copper catalyst utilizes a displacement reaction to load the silver source solution on the surface of the carbonized raney copper catalyst. The carbonized Raney copper catalyst comprises continuous phase carbon and dispersed phase Raney alloy particles, wherein the dispersed phase Raney alloy particles are uniformly or non-uniformly dispersed in the continuous phase carbon, and the continuous phase carbon is obtained by carbonizing a carbonizable organic matter or a mixture thereof; the raney alloy comprises metallic copper and elemental aluminium which can be leached.
The application method of the invention adopts the technical scheme that:
adopting silver-carbonized Raney copper catalyst, at the reaction inlet temperature of 30-60 ℃, the reaction pressure of 0.5-2.0 MPa and the reaction space velocity measured by the liquid volume of the carbon four-fraction of 2-20 h-1Removing alkyne in the liquid phase carbon four-fraction to below 30ppm under the condition that the volume ratio of hydrogen to alkyne is 0.2-10 mol/mol, and controlling the loss rate of 1, 3-butadiene to below 3%
The essential difference between the present invention and the prior art is that,
(1) the reaction space velocity of the alumina-supported copper catalyst is low<6h-1) The catalyst adopted by the invention can be used at high space velocity (space velocity)>10h-1) The method has the advantages that the selective hydrogenation alkyne removal reaction is carried out on the basis of carbon four, and the loss rate of 1,3 butadiene is low.
(2) The Raney alloy particles are distributed in the gaps of the carbon, and the porous carbon structure effectively disperses the Raney alloy particles, so that the sintering of the Raney alloy particles is reduced as much as possible in the high-temperature reaction process, and the service life of the catalyst is effectively prolonged. And the density of the carbonized Raney copper catalyst is smaller due to the loose structure of the carbonized Raney copper catalyst. The mass of the same volume of the raney copper carbide catalyst is much less than the mass of the raney copper catalyst.
(3) The silver-carbonized raney copper catalyst prepared by taking organic amine as a complexing agent avoids the hydrolysis problem of taking nitrate as a silver source, can accurately control the content of silver on the surface of carbonized raney copper, and improves the dispersion degree of the silver on the surface of the carbonized raney copper.
(4) The silver-organic amine complex reduces the usage amount of silver in the reaction, and has the characteristics of cost saving, high efficiency and the like.
The invention has the beneficial effects that:
after being activated, the silver modified Raney copper carbide alloy particles have high-dispersion copper particles, high utilization rate of active components, high hydrogenation activity and high operation airspeed; the silver modified Raney copper carbide catalyst realizes high copper loading capacity, silver can isolate active components of metal copper, the service life of the catalyst is effectively prolonged, and the loss rate of 1, 3-butadiene is reduced by doping of the silver.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials used in the examples are all commercially available.
Example 1
(1) 100 parts by mass of liquid epoxy resin (ba ling petrochemical, CYD-128), 85 parts by mass of curing agent methyl tetrahydrophthalic anhydride (MeTHPA) (Kyoto Kodak trade Co., Ltd., Guangdong Shengshida), and 1.5 parts by mass of curing accelerator Triethanolamine (TEA) (Tianjin chemical reagent Co., Ltd.) were uniformly stirred.
(2) Weighing 50g of the epoxy system prepared in the step (1) and 150g of copper-aluminum alloy powder, fully stirring and mixing, wherein the Cu content in the copper-aluminum alloy is 50% (weight), the Al content is 50% (weight), adding a proper amount of mixture into a cylindrical mold, molding for 30mins by using a flat-plate vulcanizing instrument under the conditions of 120 ℃ and 7MPa, molding for 90mins by using a flat-plate vulcanizing instrument under the conditions of 150 ℃ and 7MPa, cooling and taking out to obtain a cylindrical catalyst precursor with the diameter of about 2.0mm × 3.0.0 mm;
(3) measuring 100ml of catalyst precursor, putting the catalyst precursor into a tubular high-temperature electric furnace, keeping the temperature at the rate of 10 ℃/min and the carbonization temperature at 950 ℃ for 2 hours under the protection of nitrogen, wherein the nitrogen flow is 200ml/min, and cooling under the protection of nitrogen to obtain the copper-aluminum carbide alloy;
(4) preparing 20% NaOH aqueous solution (the mass of sodium hydroxide is 100g) by using deionized water, adding 50m L of the copper aluminum carbide alloy obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated Raney copper carbide catalyst, washing until the pH of a washing solution is 8, and storing the washing solution in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 5:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L (about 15g) of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 5m L (the content of silver is 15mg and accounts for 0.1 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence) to obtain the silver-Raney copper carbide catalyst with the content of silver on the surface of the catalyst of 0.28 wt%.
Example 2
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 20% NaOH aqueous solution (the mass of sodium hydroxide is 100g) by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated carbon raney copper catalyst, and storing the washing liquid with the pH value of 8 in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 5:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L (about 15g) of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 5m L (the silver content is 15mg and accounts for 0.1 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the silver content in the catalyst by using XRF (X-ray fluorescence), wherein the content of the silver on the surface of the catalyst is 0.24 wt%.
Example 3
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 150g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed stirrer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 6 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 5:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L (about 15g) of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 15m L (the silver content is 45mg and accounts for 0.3 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the silver content in the catalyst by using XRF (X-ray fluorescence), wherein the content of the silver on the surface of the catalyst is 0.73 wt%.
Example 4
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 600 g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed stirrer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 5:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 13m L (the silver content is 39mg and accounts for 0.26 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the silver content in the catalyst by using XRF (X-ray fluorescence), wherein the content of the silver on the surface of the catalyst is 0.96 wt%.
Example 5
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 5:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 26m L (the content of silver is 78mg and accounts for 0.52 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-carbonized raney copper catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence spectroscopy), wherein the content of silver on the surface of the catalyst is 1.86 wt%.
Example 6
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 0.5m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of ethylene diamine to silver is 1: 1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 15m L (the content of silver is 45mg and accounts for 0.3 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence) to obtain the content of silver on the surface of the catalyst, wherein the content of silver on the surface of the catalyst is 0.69 wt%.
Example 7
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 4.6m L (ethylene diamine density is 0.9g/m L) of ethylene diamine solution, dropwise adding the ethylene diamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of the ethylene diamine to the silver is 10:1, dropwise adding the ethylene diamine solution into the silver nitrate solution to form transparent and uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 15m L (the content of silver is 45mg and accounts for 0.3 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence) to obtain the content of silver on the surface of the catalyst, wherein the content of silver on the surface of the catalyst is 0.56 wt%.
Example 8
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 1.9m L (triethanolamine density is 1.1g/m L) of triethanolamine solution, dropwise adding the triethanolamine solution into 10m L deionized water to prepare uniform solution, wherein the molar ratio of the triethanolamine to the silver is 2:1, dropwise adding the triethanolamine solution into the silver nitrate solution to form transparent uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form 3.0mg Ag/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 15m L (the content of silver is 45mg and accounts for 0.3 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence) to obtain the content of silver on the surface of the catalyst, wherein the content of silver on the surface of the catalyst is 0.68 wt%.
Example 9
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing a silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the silver nitrate is dissolved, weighing 1.9m L (isopropylamine density is 0.7g/m L) of isopropylamine solution, dropwise adding the isopropylamine solution into 10m L deionized water to prepare a uniform solution, wherein the molar ratio of the isopropylamine to the silver is 4: 1, dropwise adding the isopropylamine solution into the silver nitrate solution to form a transparent uniform solution, and quantitatively adding the solution into a 200m L volumetric flask to form a 3.0mgAg/m L silver source solution.
(6) Weighing 30m L [ about 15g ] of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water, dropwise adding 15m L (the content of silver is 45mg and accounts for 0.3 wt% of the mass of the catalyst) of the silver source solution obtained in the step (1), reacting for 2 hours, filtering the solution to obtain a silver-Raney copper carbide catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence) to obtain the content of silver on the surface of the catalyst, wherein the content of silver on the surface of the catalyst is 0.71 wt%.
Example 10
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing a silver solution, namely weighing 1.2g (molar weight: 7.1mmol) of silver nitrate, adding 10m L aqueous solution of deionized water, stirring until the solution is dissolved, dropwise adding a palladium chloride hydrochloric acid solution (palladium content is 50mg/m L) 8m L, weighing 2.3m L (ethylenediamine density: 0.9g/m L and molar weight of ethylenediamine: 38mmol) of an ethylenediamine solution, dropwise adding the ethylenediamine solution into 10m L deionized water to prepare a uniform solution, wherein the molar ratio of ethylenediamine to silver is 5:1, and the molar ratio of ethylenediamine to Pd is 10:1, dropwise adding the ethylenediamine solution into the solution of silver nitrate and palladium chloride to form a transparent and uniform solution, and quantitatively accommodating the solution into a 200m L volumetric flask to form a silver source solution of 2.0mgPd/m L and 3.0mgAg/m L.
(6) Weighing 30m L (about 15g) of Raney copper catalyst, adding the Raney copper catalyst into 50m L deionized water, dropwise adding 15m L (the silver content is 45mg, the palladium content is 30mg, the silver accounts for 0.3 wt% of the catalyst mass, and the palladium accounts for 0.2 wt% of the catalyst mass) of the silver source solution in the step (5), filtering the solution after reacting for 2 hours, detecting the silver content in the catalyst by XRF to obtain the silver-Raney copper carbide catalyst, wherein the silver content on the surface of the catalyst is 0.73 wt%, and the palladium content is 0.12 wt%.
Example 11
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney copper carbide catalyst, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(5) Preparing a silver solution: weighing AgNO31.2g (molar mass: 7.1mmol), Ni (NO)3)2·6H2O11g (molar weight: 38mmol) is added into deionized water 50m L water solution and stirred until dissolved, 20m L of palladium chloride hydrochloric acid solution (palladium content 50mg/m L) is added dropwise, ethylene diamine solution 2.3m L (ethylene diamine density 0.9g/m L, molar weight of ethylene diamine: 38mmol) is weighed and added into 10m L deionized water to prepare uniform solution, the molar ratio of ethylene diamine to silver is 5:1, the molar ratio of ethylene diamine to Ni is 1: 1, the molar ratio of ethylene diamine to Pd is 4: 1, transparent and uniform solution is formed, the solution is fixed in a 200m L volumetric flask to form silver source solution of 3.0mgAg/m L, 10mgNi/m L and 5.0mgPd/m L.
(6) Weighing 30m L (about 15g) of Raney copper catalyst, adding the Raney copper catalyst into 50m L deionized water, dropwise adding 15m L (the silver content is 45mg, the nickel content is 150mg, and the Pd content is 75 mg; the silver content is 0.3 wt% of the catalyst mass, the nickel content is 1.0 wt% of the catalyst mass, and the palladium content is 0.5 wt% of the catalyst mass) of the silver source solution in the step (5), reacting for 2 hours, filtering the solution, detecting the silver content in the catalyst by XRF to obtain the silver-Raney copper catalyst, wherein the silver content on the surface of the catalyst is 0.73 wt%, the palladium content is 0.28 wt%, and the nickel content is 0.89 wt%.
Comparative example 1
And (2) crushing the copper-aluminum alloy into alloy blocks of about 0.9-3.2mm, slowly adding the alloy blocks into a 20% sodium hydroxide solution in batches, and activating for 2h, wherein the catalyst treated by the steps is washed for 20-40 times by using deionized water at the temperature of 20-40 ℃ for 1000m L until the pH value of a washing liquid is 7-9.
Comparative example 2
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney's copper carbide catalyst, washing the catalyst to be nearly neutral, and storing the catalyst in the deionized water for later use.
(5) Preparing silver solution, namely weighing 15.6g of silver nitrate, dissolving the silver nitrate into a 100m L volumetric flask, and fixing the volume, wherein the content of silver is 100mg/m L.
(6) 30m L (about 15g) of the catalyst obtained in the step (4) is weighed and added into 50m L deionized water solution, 5m L (the silver content is 500mg, and the silver accounts for 3.3 wt% of the catalyst) of silver nitrate solution in the step (5) is added, the solution is filtered after 2 hours of reaction, and the silver content in the final catalyst is 1.38 wt%.
Comparative example 3
(1) Fully mixing powdery phenolic resin and curing agent hexamethylenetetramine by using a high-speed stirrer, wherein the weight ratio of the hexamethylenetetramine to the phenolic resin is 12/100; fully mixing 100g of the mixture with 300 g of copper-aluminum alloy powder by using a high-speed mixer, wherein the Cu content in the copper-aluminum alloy is 50 percent (by weight), and the aluminum content is 50 percent (by weight);
(2) heating a tablet machine to 90 ℃, putting the materials into a die, and carrying out die pressing on the tablet machine to form a sheet with the thickness of 2 mm; heating the tablet press to 150 ℃, putting the formed sheet into the die again, and curing for 10min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into rectangular small particles with the thickness of 3-5 mm;
(3) weighing 100m L small particles, carbonizing in a tubular high-temperature electric furnace at a heating rate of 10 ℃/min and a furnace temperature of 650 ℃, keeping for 3 hours, and protecting with nitrogen at a flow rate of 200m L/min;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain the activated Raney's copper carbide catalyst, washing the catalyst to be nearly neutral, and storing the catalyst in the deionized water for later use.
(5) Preparing silver solution, namely weighing 15.6g of silver nitrate, dissolving the silver nitrate into a 100m L volumetric flask, and fixing the volume, wherein the content of silver is 100mg/m L.
(6) Weighing 30m L of the catalyst obtained in the step (4), adding the catalyst into 50m L deionized water solution, adding 8m L of silver nitrate solution (the silver content is 800mg, and accounts for 5.3 wt% of the mass of the catalyst) in the step (5), reacting for 2 hours, and filtering the solution to obtain the final catalyst with the silver content of 0.89 wt%.
Comparative example 4
Weighing 102g Cu (NO)3)2·3H2O,174g Al(NO3)3·9H2Preparing a mixed salt solution of copper nitrate and aluminum nitrate with the concentration of 2.0M by using O, stirring and mixing the mixed solution evenly to obtain a mixed solution, adding 15M L into the mixed solution, adding the mixed solution into 9M L (the Ag content is 100mg/M L) of the silver nitrate solution prepared in the step (3) in the embodiment 1, weighing 50g of NaOH into 200M L deionized water, slowly pouring the sodium hydroxide solution into the mixed solution of the three metal salts under continuous stirring, adjusting the pH value to be neutral, filtering the solution, washing the solution with the deionized water for three times, filtering the solution, drying the solution in a drying box at the temperature of 100 ℃ for overnight, roasting the solution at the temperature of 400 ℃ for 5 hours, tabletting and forming the solution, wherein the obtained Cu content is about 40%, and the Ag content is 2.
Example 12
The prepared catalyst was subjected to a fixed bed test under the following reaction conditions:
the reactor is a two-section fixed bed reactor, each section is filled with 10m L of catalyst, the catalyst is filled into the reactor, nitrogen is used for conversion, the carbon four fraction is added with hydrogen and then is introduced into the reactor, the composition (fraction) of the carbon four fraction is shown in table 1, the reaction conditions are that the hydrogen pressure is 1.0Mpa, the inlet temperature of the two-section reactor is 45 ℃, the molar ratio of hydrogen to alkyne is 2-4, and the liquid hourly space velocity is 10-20h-1. The content of each component in the carbon four fraction was determined by gas chromatography.
The carbon four-fraction selective hydrogenation catalytic performance of the catalyst was evaluated, wherein examples 1 to 4 and comparative examples 1 to 3 were directly evaluated, and before evaluation of comparative example 4, the catalyst was reduced by purging with hydrogen at 150 ℃ for 2 hours, and the total acetylene content and butadiene loss after carbon four-hydrogenation of each catalyst at 45 ℃ were as shown in Table 2.
Figure BDA0001130903400000191
Figure BDA0001130903400000192
TABLE 1 raw material composition of C4
Components Raw material content (wt%) Components Raw material content (wt%)
Isobutane 2.30 1, 2-butadiene -
N-butane 6.33 1, 3-butadiene 48.19
Trans-2-butene 4.14 Methylacetylene 0.10
1-butene 12.69 Ethyl acetylene 0.76
Isobutene 22.97 Vinyl acetylene 0.12
Cis-2-butene 2.31
TABLE 2 results of the C-Tetra-Selective Hydrocarbon Deacetylene test
Figure BDA0001130903400000201
The results of the acetylene removal by carbon-tetra hydrogenation test can be obtained as follows:
the silver-loaded Raney copper catalyst prepared by using organic amine as a complexing agent can be high in contentAt space velocity of (>10h-1) Removing the alkyne in the inlet carbon four-fraction to be below 30ppm, and controlling the loss rate of 1, 3-butadiene to be below 3.0%;
the doping amount of silver can be accurately controlled by using the organic amine solution to stabilize the silver complex as the silver source, while the doping amount of silver cannot be accurately controlled by using the silver nitrate as the silver source to prepare the silver-modified Raney copper catalyst.
The loss of 1, 3-butadiene is higher (> 3%) for silver-carbonized raney-copper catalysts and unmodified raney-copper catalysts prepared using silver nitrate as the silver source. The silver-carbonized raney copper catalyst, although slightly reduced in activity, effectively reduced the loss of 1, 3-butadiene compared to the raney copper catalyst. While the copper-based catalyst (comparative example 4) using alumina as a carrier was remarkably insufficient in acetylene removing ability at a high space velocity.

Claims (10)

1. A preparation method of a silver-carbonized Raney copper catalyst is characterized by comprising the following steps:
(1) uniformly mixing the Raney alloy particles with a curing system of a carbonizable organic substance, and then curing to obtain a catalyst precursor; the weight ratio of the Raney alloy particles to the organic matter curing system capable of being carbonized is 1: 99-99: 1;
the curing system of the carbonizable organic matter comprises the carbonizable organic matter and additives; the organic matter capable of being carbonized is an organic high molecular compound;
(2) carbonizing the obtained catalyst precursor at high temperature under the protection of inert gas, and activating to obtain a carbonized raney copper catalyst;
(3) preparing a mixed solution of soluble organic amine and water, and dissolving soluble silver salt and soluble salts of other assistants to prepare a silver source solution;
the molar ratio of the soluble organic amine to the silver salt solution is 1: 1-10: 1;
other auxiliary agents comprise one or more of Co, Fe, Mn, Ni, Zn, Cr and Pd;
the mol ratio of the soluble organic amine to the auxiliary agent is 1: 2-10: 1;
the soluble organic amine is one or more of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, dodecylamine, triethylenediamine, cyclohexylamine and hexamethylenetetramine;
(4) adding a Raney copper carbide catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (3) into the Raney copper carbide catalyst solution, reacting for 1-2 hours, and washing to obtain a silver Raney copper carbide catalyst;
the mass of the silver in the silver source solution is 0.01 w-1.0 wt% of that of the Raney copper carbide catalyst;
the mass of the auxiliary metal in the silver source solution is 0-5 wt% of the Raney copper carbide catalyst.
2. The method of preparing a silver-carbonized raney copper catalyst of claim 1, characterized in that:
the organic high molecular compound is at least one of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, starch, viscose fiber, lignin, cellulose, styrene butadiene rubber and polyurethane rubber;
the additive is one or the combination of a curing accelerator, a dye, a pigment, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant, a flow modifier or auxiliary agent, a flame retardant, an anti-dripping agent, an anti-caking agent, an adhesion promoter, a conductive agent, a polyvalent metal ion, an impact modifier, a demolding auxiliary agent and a nucleating agent;
the soluble organic amine is one or more of triethanolamine, ethanolamine, ethylenediamine and hexamethylenediamine.
3. The method of preparing a silver-carbon raney copper catalyst of claim 2, which comprises:
the weight ratio of the Raney alloy particles to the organic matter curing system capable of being carbonized is 10: 90-90: 10;
the molar ratio of the soluble organic amine to the silver salt solution is 2: 1-5: 1;
the mass of the silver in the silver source solution is 0.1-0.6 wt% of the Raney copper carbide catalyst;
the mass of the auxiliary metal in the silver source solution is 0.2-1 wt% of that of the Raney copper carbide catalyst.
4. The method of preparing a silver-carbonized raney copper catalyst of claim 3, characterized in that:
the weight ratio of the Raney alloy particles to the organic matter curing system capable of being carbonized is 25: 75-75: 25.
5. the method of preparing a silver-carbonized raney copper catalyst of claim 1, characterized in that:
the carbonization temperature in the step (2) is 400-1200 ℃; and the protective gas is nitrogen or argon, and the carbonization is carried out for 1-12 hours.
6. The method of preparing a silver-carbonized raney copper catalyst of claim 5, characterized in that:
the carbonization temperature in the step (2) is 600-950 ℃.
7. The method of preparing a silver-carbon raney copper catalyst of claim 6, which comprises:
in the step (3), the soluble salt of silver is nitrate, and the other auxiliary agent soluble salt is nitrate, chloride or acetate.
8. The method of preparing a silver-carbonized raney copper catalyst of claim 1, characterized in that:
raney alloys include metallic copper and metallic aluminum.
9. A silver-carbonized Raney copper catalyst prepared by the process of any one of claims 1 to 8.
10. Use of a silver-carbonized raney copper catalyst prepared according to any one of claims 1 to 8 in the dehydrogenation of alkynes from carbon tetrahydride, characterized in that:
the reaction inlet temperature is 30-60 ℃, the reaction pressure is 0.5-2.0 MPa, and the reaction space velocity measured by the liquid volume of the carbon four-fraction is 2-20 h-1Under the condition of (1), acetylene hydrocarbon in the liquid phase carbon four fraction is removed to be below 30ppm, and the loss rate of 1, 3-butadiene is controlled to be below 3 percent.
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CN111085222A (en) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 Silver-zinc carbon raney copper catalyst and preparation method and application thereof
CN111085223A (en) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 Silver-loaded-zinc-doped Raney copper catalyst and preparation method and application thereof
CN111085221A (en) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 Silver-zinc doped Raney copper catalyst and preparation method and application thereof
CN112791734B (en) * 2019-10-28 2022-09-20 中国石油化工股份有限公司 Silver and nitrogen doped Raney copper zinc carbide catalyst and preparation method and application thereof
CN112791733A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Preparation method of silver-carbonized raney copper catalyst, catalyst and application
CN114452993A (en) * 2020-10-22 2022-05-10 中国石油化工股份有限公司 Preparation method of Raney copper carbide catalyst, catalyst and method for preparing ethanol by acetate hydrogenation

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