CN107952451A - A kind of preparation method, catalyst and the application of silver loaded catalyst - Google Patents

A kind of preparation method, catalyst and the application of silver loaded catalyst Download PDF

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Publication number
CN107952451A
CN107952451A CN201610899855.1A CN201610899855A CN107952451A CN 107952451 A CN107952451 A CN 107952451A CN 201610899855 A CN201610899855 A CN 201610899855A CN 107952451 A CN107952451 A CN 107952451A
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silver
catalyst
solution
raney
supported catalyst
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王秀玲
吴佳佳
乐毅
鲁树亮
张晓红
彭晖
蒋海斌
刘海江
汪晓菁
郝雪松
徐洋
戴伟
乔金樑
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation method, catalyst and the application of silver-colored loaded catalyst.Method includes：(a) high-molecular organic material carrier and Raney alloy particle are prepared into loaded catalyst；(b) loaded catalyst is activated using sodium hydroxide solution；(c) soluble organic amine and water are made into mixed solution, are redissolved soluble silver salt and the soluble-salt of other auxiliary agents, are prepared into silver-colored source solution；(d) loaded catalyst is added in deionized water and aaerosol solution is formed by stirring, silver-colored source solution in above-mentioned steps (c) is added dropwise in load type Reni copper catalyst solution, silver loaded catalyst is made when reaction 1~2 is small, after washing.Alkynes in liquid phase c4 fraction can be removed to below 30ppm by the catalyst of the present invention, and 1,3 butadiene loss late is controlled below 3%.

Description

Preparation method of silver supported catalyst, catalyst and application
Technical Field
The invention relates to the field of selective hydrogenation alkyne removal catalysts, in particular to a preparation method of a silver supported catalyst, the catalyst and application.
Background
Selective hydrogenation of the four carbon cuts to remove alkynes is a more economical process than extractive distillation. 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 alkyne removal, and the patent US4440956 indicates that the copper-based catalyst used for carbon four-selective hydrogenation alkyne removal has the advantages of less butadiene loss, good selectivity, low space velocity, short service life and frequent regeneration on the premise of removing indexes. The catalyst adopted by the industrialized U.S. DOW KLP technology is a copper catalyst, ten sets of devices are built all over the world, and the catalyst adopted by the KLP technology also has the problems of frequent regeneration, low airspeed and the like. Although there are many documents and patents, such as patent CN103170349, US3912789A, which relate to the addition of promoter metals to improve the selectivity and stability of the catalyst, the problem of low space velocity of the catalyst still remains unchanged. Therefore, the development of the Cu catalyst with high space velocity and high selectivity has great significance for the application of the carbon four selective hydrogenation technology.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a silver supported 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 supported catalyst.
The method comprises the following steps:
(a) preparing a supported catalyst from an organic high polymer material carrier and Raney alloy particles;
(b) activating the supported catalyst by using a sodium hydroxide solution;
(c) 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 (1-10): 1, preferably (2-5): 1.
Other auxiliary agents comprise one or more of Co, Fe, Mn, Ni, Zn, Cr and Pd;
the mol ratio of the organic amine to the auxiliary agent is 1: 2-10: 1;
(d) adding the supported catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (c) into the supported Raney's copper catalyst solution, reacting for 1-2 hours, and washing to obtain the silver supported catalyst.
The mass of the silver in the silver source solution is 0.05 wt% -1.0 wt%, preferably 0.1 wt% -0.7 wt% of the Raney copper catalyst.
The mass of the auxiliary agent in the silver source solution is 0-5 wt% of the supported Raney copper catalyst, and preferably 0-2 wt%
The raney alloy comprises raney metal and leachable elements; the weight ratio of raney metal to leachable elements is 1: 99-10: 1; preferably 1: 10-4: 1;
the organic polymer material is plastic or a modified product thereof;
plastics include thermosets and thermoplastics.
In step a, the preparation of the supported catalyst comprises:
under the condition of organic high polymer material forming and processing temperature or under the condition of uncured shaping, the die pressing is coated by the Raney alloy particles.
In particular, the amount of the solvent to be used,
when the organic polymer material is thermoplastic, placing thermoplastic particles in the Raney alloy particles, or coating the Raney alloy particles on a thermoplastic sheet, and molding to obtain the supported catalyst.
When the organic polymer material is thermosetting plastic, firstly preparing a thermosetting plastic curing system;
adding the Raney alloy powder into the mould, then adding the thermosetting plastic curing system, then adding the Raney alloy powder, carrying out partial curing and shaping, and then continuing mould pressing and curing the partially cured and shaped granular carrier coated with the Raney alloy powder to obtain the supported catalyst.
Or,
and (3) molding the thermosetting plastic curing system into a sheet, incompletely curing, uniformly coating the Raney alloy powder on the upper surface and the lower surface, and continuously molding until the complete curing is achieved to obtain the supported catalyst.
In step b, conventional methods in the prior art are adopted, such as:
in the activation process, the supported Raney copper catalyst is not limited by a fixed mesh number, and preferably 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.
The soluble organic amine is preferably one or more of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, dodecylamine, triethylenediamine, cyclohexylamine and hexamethylenetetramine; more preferably one or more of triethanolamine, ethanolamine, ethylenediamine and hexamethylenediamine.
The soluble salt of silver is nitrate;
other soluble auxiliary agent salts are nitrate, chloride or acetate
The second purpose of the invention is to provide a silver supported catalyst prepared by the method.
The invention also aims to provide the application of the silver supported catalyst prepared by the method in the alkyne removal by carbon tetrahydrogenation.
The preparation method of the invention adopts the technical scheme that:
(a) preparing a supported catalyst from an organic high polymer material carrier and Raney alloy particles;
(b) activating the supported catalyst by using a sodium hydroxide solution;
(c) 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.
(d) Adding the supported Raney copper catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (c) into the supported Raney copper catalyst solution without adjusting the pH value or any reducing agent, reacting for 1-2 hours, taking out the catalyst, and washing with deionized water for three times for later use.
The supported catalyst in the step (a) comprises an organic polymer material carrier and Raney alloy particles loaded on the surface of the organic polymer material carrier, wherein the Raney alloy comprises Raney metallic copper and aluminum which is a leachable element.
The Raney alloy particles are loaded on the surface of a carrier in a form of being partially embedded into an organic high polymer material carrier. The phrase "the particles of the raney alloy are partially embedded in the support of the organic polymer material" means that each particle of the raney alloy has a portion embedded in the support.
The part of the Raney alloy particles is embedded into the organic polymer material carrier by molding the carrier coated by the Raney alloy particles at the carrier molding processing temperature or under the uncured shaping condition. Under the double action of heat and pressure, the carrier of organic polymer material is softened and deformed, the Raney alloy particles are partially pressed into the softened carrier, the softened carrier overflows around the particles while the particles are partially pressed, the overflowing carrier not only plays a role of firmly fixing the particles, but also presses other particles into the surface of the overflowing carrier, and the steps are repeated, so that the Raney alloy particles are partially pressed into all the surfaces of the carrier which can be pressed. As described above, the present invention effectively utilizes the surface area of the carrier, so that the active metal content supported by the catalyst is high. In addition, because the particles of the Raney alloy are partially embedded in the carrier, the carrier around the particles serves as a firm fixture, so that the catalyst has good stability.
The raney alloy includes raney metal and a leachable element. "Raney metal" means a metal that is insoluble when activated by Raney process, and most typically the Raney metal is at least one of nickel, cobalt, copper and iron. "leachable elements" refers to elements that are soluble when activated by the raney process, and typically are at least one of aluminum, zinc, and silicon. The Raney alloy is preferably copper aluminum alloy.
The invention does not require the particle size and the component content of the Raney alloy, and the commercially available Raney alloy can be used, and the average particle size of the particles of the commercially available Raney alloy is generally 0.1-1000 microns, preferably 10-100 microns. The weight ratio of raney metal to leachable elements is 1: 99-10: 1, preferably in a weight ratio of 1: 10-4: 1. the organic polymer material is preferably plastic or a modified product thereof, and the plastic comprises thermosetting plastic and thermoplastic plastic. The specific plastic comprises: polyolefin, poly-4-methyl-1-pentene, polyamide resin (e.g., nylon-5, nylon-12, nylon-6/6, nylon-6/10, nylon-11), polycarbonate resin, linear polyester obtained by polycondensation of homo-and/or co-polyoxymethylene, saturated dibasic acid and dihydric alcohol, aromatic ring polymer (polymer whose molecule consists only of aromatic ring and linking group, such as polyphenyl, polyphenylene ether, polyphenylene sulfide, polyarylsulfone, polyaryl ketone, polyaryl ester, aromatic polyamide), heterocyclic polymer (polymer material whose main chain of molecule has heterocyclic ring in addition to aromatic ring, such as polybenzimidazole), fluorine-containing polymers, acrylic resins, urethanes, epoxy resins, phenol resins, urea resins, melamine resins, and the like. At least one of polyolefin resin, polyamide resin, polystyrene, epoxy resin and phenol resin is preferable, and at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenol resin and epoxy resin is more preferable.
The plastic modified product refers to a modified product obtained by adopting the existing plastic modification method. Plastic modification methods include, but are not limited to, the following: graft modification of polar or non-polar monomers or polymers thereof; the material is modified by melt blending with inorganic or organic reinforcing materials, toughening materials, stiffening materials, heat resistance increasing materials and the like.
The preparation method of the supported catalyst comprises the following steps: and under the condition of the forming processing temperature of the organic polymer material or the uncured shaping condition, the organic polymer material coated by the Raney alloy particles is molded.
The specific preparation method is slightly different for different organic polymer material carriers.
When the carrier is a thermoplastic organic polymer material, the following method (i) or (ii) can be specifically selected:
method (i):
(1) processing the thermoplastic carrier into particles of any shape according to the size required by the fixed bed catalyst or the fluidized bed catalyst;
(2) placing the carrier particles in the Raney alloy particles, namely, the carrier is completely coated by the Raney alloy particles;
(3) and under the condition of corresponding thermoplastic carrier forming processing temperature, placing the thermoplastic carrier in the Raney alloy particles by die pressing, partially pressing the Raney alloy particles into the thermoplastic carrier particles to load the Raney alloy particles on the surfaces of the thermoplastic carrier particles and partially embed the Raney alloy particles into the carrier, cooling and sieving to obtain the granular supported catalyst.
The particle size of the particulate supported catalyst is based on the particle size that can meet the requirements of a fixed bed catalyst or a fluidized bed catalyst. The shape of the particles may be any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, tooth shape or a combination of the above shapes, etc., preferably spherical, ring, tooth shape, cylindrical or a combination of the above shapes. The thermoplastic carrier particles can be shaped from powder or can be used directly as commercially available shaped thermoplastic carrier particles.
Or method (ii):
(1) processing the thermoplastic carrier into a sheet with the thickness required by the fixed bed catalyst or the fluidized bed catalyst;
(2) uniformly coating the surface of the obtained carrier sheet with the Raney alloy particles;
(3) the method comprises the steps of carrying out die pressing on a sheet material coated by the Raney alloy particles under the common molding processing temperature condition of a corresponding thermoplastic carrier, pressing part of the Raney alloy particles into the carrier sheet material, cooling, processing the carrier sheet material with the Raney alloy particles loaded on the surface into particles with required shape and size by cutting, stamping or crushing and other methods by adopting any available processing equipment, and finally obtaining the granular supported catalyst.
The thermoplastic carrier described in method (i) or method (ii) may incorporate additives commonly used in plastics processing such as antioxidants, secondary antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, softeners, antiblocking agents, blowing agents, dyes, pigments, waxes, extenders, organic acids, flame retardants, and coupling agents. The dosage of the used auxiliary agent is conventional dosage or is adjusted according to the requirements of actual conditions.
When the support is a thermosetting organic polymer material support, the following method (iii) or (iv) can be specifically selected for preparation:
method (iii):
(1) preparing a proper curing system according to a common curing formula of a thermosetting carrier, wherein a liquid system can be directly and uniformly stirred; 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.
(2) Adding Raney alloy powder into a die with any cavity shape which can meet the particle size required by a fixed bed catalyst or a fluidized bed catalyst, then adding the prepared uncured thermosetting organic high polymer material, then adding the Raney alloy powder, carrying out partial curing and shaping under the common curing condition, then carrying out mould pressing and curing on the partially cured and shaped granular carrier coated with the Raney alloy powder by any available organic high polymer material processing equipment, and sieving after complete curing to obtain the granular supported catalyst;
or method (iv):
(1) preparing a proper curing system according to a common curing formula of the thermosetting organic high polymer material, wherein a liquid system can be directly and uniformly stirred; 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.
(2) Under the common curing condition, the prepared thermosetting organic polymer material system is molded into a sheet by any available equipment, the sheet is not cured completely, the thickness is determined by the size of a fixed bed catalyst or a fluidized bed catalyst, the upper surface and the lower surface of the sheet are uniformly coated with Raney alloy powder, the sheet is molded continuously until the sheet is cured completely, the Raney alloy powder is partially pressed into a thermosetting carrier, and the surface of the thermosetting carrier sheet is loaded by the Raney alloy powder, so that the loaded catalyst is obtained.
(3) The obtained supported catalyst is 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 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 the fixed bed catalyst or the fluidized bed catalyst, 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, and the preferred shape is spherical, annular, tooth shape, cylindrical or the combination of the shapes.
In the preparation of the thermosetting organic polymer material curing system according to the method (iii) or the method (iv), optionally, one or more additives selected from the group consisting of: 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.
In the step (b), the supported Raney copper catalyst is not limited by a fixed mesh number in the activation process, and preferably 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 step (c), the soluble salt of silver is nitrate, and the other soluble salt of the auxiliary agent is nitrate, chloride or acetate.
In step (c), 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, preferably one or more of triethanolamine, ethanolamine, ethylenediamine, and hexamethylenediamine.
In the step (d), the silver modified Raney copper carbide catalyst is prepared by loading a silver source solution on the surface of a supported Raney copper catalyst by using a displacement reaction.
The application method of the invention adopts the technical scheme that:
adopting a silver-modified supported Raney copper catalyst, wherein 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-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%.
The essential difference between the present invention and the prior art is that,
(1) the reaction space velocity of the copper catalyst taking alumina as the carrier is low (<6h-1) In the following, the silver supported Raney copper catalyst of the present invention can be used at a 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 copper catalyst loaded with silver prepared by using organic amine as a complexing agent can accurately control the content of silver on the surface of raney copper and improve the dispersion degree of silver on the surface of raney copper.
(3) The hydrolysis of silver nitrate in a system is avoided, the silver-organic amine complex reduces the usage amount of silver in the reaction, and the characteristics of cost saving, high efficiency and the like are achieved.
The invention has the beneficial effects that:
(1) after being activated, the silver modified load type Raney copper alloy particles have high-dispersion copper particles, high utilization rate of active components, high hydrogenation activity and high operation airspeed;
(2) compared with a raney copper catalyst and a silver-raney copper catalyst prepared by taking silver nitrate as a silver source, the silver-modified supported raney copper catalyst prepared by taking organic amine silver as the silver source has better selectivity and low butadiene loss rate in the carbon four selective hydrogenation reaction;
(3) the raney copper catalyst is modified by silver to realize high copper loading capacity, and the silver can isolate the active component of metal copper, so that the service life of the catalyst is effectively prolonged, and the loss rate of 1, 3-butadiene is reduced by doping the silver.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of aqueous solution, dropwise adding 7mL (the content of silver is 21mg, and accounts for 0.12 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence microscopy) to obtain the content of silver on the surface of the catalyst, wherein the content of silver on the surface of the catalyst is 0.28 wt%.
Example 2
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of the ethylenediamine to the silver is 5: 1, the solution of the ethylenediamine is dropwise added into the silver nitrate solution to form a transparent and uniform solution, and the solution is placed in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.65 wt%.
Example 3
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of the ethylenediamine to the silver is 5: 1, the solution of the ethylenediamine is dropwise added into the silver nitrate solution to form a transparent and uniform solution, and the solution is placed in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 28mL (the content of silver is 74mg, and accounts for 0.41 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.89 wt%.
Example 4
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 40mL (the content of silver is 120mg, and accounts for 0.67 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 1.38 wt%.
Example 5
(1) Weighing 50g of powdery phenolic resin, placing the powdery phenolic resin into a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt%, the Al content is 50 wt%, carrying out mould pressing for 10min at the temperature of 220 ℃ and under the pressure of 7MPa by using a flat vulcanizing machine, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and obtaining a supported catalyst, wherein the weight is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of aqueous solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.67 wt%.
Example 6
(1) Weighing 50g of epoxy resin, placing the epoxy resin into a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt%, the Al content is 50 wt%, carrying out die pressing for 10min by using a flat vulcanizing machine under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and obtaining a supported catalyst, wherein the weight is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 2.3mL of ethylenediamine solution (the density of ethylenediamine is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of aqueous solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.62 wt%.
Example 7
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 1.9mL of triethanolamine solution (density of triethanolamine is 1.1g/mL), and dropwise adding the triethanolamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of triethanolamine to silver is 2: 1, dropwise adding a solution of triethanolamine into a silver nitrate solution to form a transparent and uniform solution, and quantitatively accommodating the solution in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.64 wt%.
Example 8
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 1.9mL of isopropylamine solution (isopropylamine density: 0.7g/mL), and dropwise adding the isopropylamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding a solution of triethanolamine into a silver nitrate solution to form a transparent and uniform solution, and quantitatively accommodating the solution in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.65 wt%.
Example 9
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 0.5mL of ethylenediamine solution (ethylenediamine density is 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 1: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.60 wt%.
Example 10
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, weighing 4.6mL of ethylenediamine solution (ethylenediamine density: 0.9g/mL), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver was 10: 1, dropwise adding the solution of ethylenediamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the content of silver is 63mg and accounts for 0.35 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the content of silver in the catalyst by using XRF (X-ray fluorescence), wherein the content of silver on the surface of the catalyst is 0.59 wt%.
Example 11
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the solution is dissolved, dropwise adding 8mL of palladium chloride hydrochloric acid solution (palladium content: 50mg/mL), weighing 2.3mL of ethylenediamine solution (ethylenediamine density: 0.9g/mL, molar weight of ethylenediamine: 38mmol), and dropwise adding the ethylenediamine solution into 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, the molar ratio of ethylenediamine to Pd is 10: 1, dropwise adding an ethylene diamine aqueous solution into a solution of silver nitrate and palladium chloride to form a transparent and uniform solution, and setting the solution in a 200mL volumetric flask to form a silver source solution of 2.0mgPd/mL and 3.0 mgAg/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the silver content is 63mg, the palladium content is 42mg, the silver accounts for 0.35 wt% of the mass of the added catalyst, and the palladium accounts for 0.23 wt% of the mass of the added catalyst) of the silver source solution in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, detecting the silver content in the catalyst by XRF, and measuring the silver content on the surface of the catalyst to be 0.65 wt% and the Pd content to be 0.12 wt%.
Example 12
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing until the pH value of washing liquor is 8, and storing in the deionized water for later use.
(3) Preparing a silver solution: weighing AgNO31.2g (molar mass: 7.1mmol), Ni (NO)3)2·6H2O11g (molar weight: 38mmol) was added to 50mL of an aqueous solution of deionized water, stirred until dissolved, and a salt of palladium chloride was added dropwise20mL of an acid solution (palladium content: 50mg/mL), 2.3mL of an ethylenediamine solution (ethylenediamine density: 0.9g/mL, molar weight of ethylenediamine: 38mmol) was weighed and added dropwise to 10mL of deionized water to prepare a uniform solution. The molar ratio of ethylenediamine to silver is 5: 1, the molar ratio of ethylenediamine to Ni is 1: 1, the molar ratio of ethylenediamine to Pd is 4: 1, forming a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a silver source solution with the concentration of 3.0mgAg/mL, 10mgNi/mL and 5.0 mgPd/mL.
(4) Measuring 30mL (about 18g) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, dropwise adding 21mL (the silver content is 63mg, the palladium content is 105mg, and the nickel content is 210mg, wherein the silver accounts for 0.35 wt% of the added catalyst mass, the palladium accounts for 0.58 wt% of the added catalyst mass, and the nickel accounts for 1.2 wt% of the added catalyst mass) of the silver source solution obtained in the step (3), reacting for 2 hours, filtering the solution to obtain a silver-supported Raney copper catalyst, and detecting the silver content in the catalyst by using XRF (X-ray fluorescence), wherein the silver content on the surface of the catalyst is 0.65 wt%, the palladium content is 0.28 wt%, and the nickel content is 0.89 wt%.
Comparative example 1
After the copper-aluminum alloy is crushed into alloy blocks with the diameter of about 0.9-3.2mm, the alloy blocks are slowly added into a 20% sodium hydroxide solution in batches, and the activation time is 2 hours. Washing the catalyst treated by the steps with 1000mL of deionized water at 20-40 ℃ for 20-40 times until the pH value of the washing liquid is 7-9.
Comparative example 2
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing the supported catalyst to be nearly neutral, and storing the activated supported catalyst in the deionized water for later use.
(3) Weighing 15.6g of silver nitrate, dissolving in a 100mL volumetric flask to a constant volume, wherein the content of silver is 100 mg/mL.
(4) Measuring 30mL (18 g of the mass of the catalyst) of the catalyst obtained in the step (2), adding the catalyst into 50mL of deionized water solution, adding 4mL (the silver content is 400mg and accounts for 2.2 wt% of the mass of the catalyst) of silver nitrate solution obtained in the step (3), reacting for 2 hours, and filtering the solution to obtain the final catalyst with the silver content of 0.72 wt%.
Comparative example 3
(1) Weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in a copper-aluminum alloy powder body, wherein the Cu content in the copper-aluminum alloy is 50 wt% and the Al content is 50 wt%, performing mould pressing for 10min by using a flat-plate vulcanizing instrument under the conditions of the temperature of 220 ℃ and the pressure of 7MPa, taking out, cooling, sieving to obtain spherical particles, completely covering the surfaces of the particles by the copper-aluminum alloy powder, and thus obtaining a supported catalyst, wherein the weight of the supported catalyst is 210 g;
(2) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1 hour to obtain an activated supported catalyst, washing the supported catalyst to be nearly neutral, and storing the activated supported catalyst in the deionized water for later use.
(3) Weighing 15.6g of silver nitrate, dissolving in a 100mL volumetric flask to a constant volume, wherein the content of silver is 100 mg/mL.
(4) 30mL (about 18g by mass) of the catalyst obtained in the step (2) is weighed and added into 50mL of deionized water solution, 7mL of silver nitrate solution (700 mg of silver, which accounts for 3.9% by mass of the catalyst) in the step (3) is added, the solution is filtered after 2 hours of reaction, and the content of silver in the final catalyst is 0.68 wt%.
Comparative example 4
Weighing 102g Cu (NO)3)2·3H2O,174g Al(NO3)3·9H2O copper nitrate and aluminum nitrate with the concentration of 2.0MAfter stirring and mixing the mixed salt solution to be uniform to obtain a mixed solution, adding 15mL of the mixed solution, adding 3mL of the silver nitrate solution prepared in the step (3) in the example 1 (wherein the Ag content is 100 mg/mL); weighing 50g of NaOH in 200mL of deionized water, slowly pouring the sodium hydroxide solution into the mixed solution of the three metal salts under continuous stirring, and adjusting the pH value to be neutral. Filtering the solution, washing with deionized water for three times, suction-filtering, drying in a drying oven at 100 deg.C overnight, roasting at 400 deg.C for 5 hr, tabletting, and forming to obtain a tablet with Cu content of about 40% and Ag content of 0.6%.
Example 13
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 10mL of catalyst, the catalyst is filled into the reactor, nitrogen is used for conversion, and the carbon four fraction is introduced into the reactor after hydrogen is added. The composition (fraction) of the carbon four fraction is shown in Table 1. The reaction conditions are as follows: the pressure of hydrogen is 1.0Mpa, the inlet temperature of the two-stage 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 1-12 and comparative examples 1-3 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.
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
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 prepared at a high space velocity>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 silver-loaded raney copper catalyst and the unmodified raney copper catalyst prepared by using silver nitrate as a silver source have high activity, but the loss of 1, 3-butadiene is high (> 3%).

Claims (9)

1. A method for preparing a silver supported catalyst, characterized in that the method comprises:
(a) preparing a supported catalyst from an organic high polymer material carrier and Raney alloy particles;
(b) activating the supported catalyst by using a sodium hydroxide solution;
(c) 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 is (1-10) to 1;
other auxiliary agents comprise one or more of Co, Fe, Mn, Ni, Zn, Cr and Pd;
the mol ratio of the organic amine to the auxiliary agent is 1: 2-10: 1;
(d) adding a supported catalyst into deionized water, stirring to form a suspension solution, dropwise adding the silver source solution obtained in the step (c) into the supported Raney's copper catalyst solution, reacting for 1-2 hours, and washing to obtain a silver supported catalyst;
the mass of the silver in the silver source solution is 0.05 wt% -1.0 wt% of that of the Raney copper catalyst;
the mass of the auxiliary agent in the silver source solution is 0-5 wt% of the mass of the Raney copper catalyst.
2. The method of preparing a silver-supported catalyst according to claim 1, wherein:
raney alloys comprise raney metallic copper and elemental aluminium which can be leached; wherein the mass ratio of copper to aluminum is 1: 1;
the organic polymer material is plastic or a modified product thereof;
plastics include thermosets and thermoplastics;
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.
3. The method of preparing a silver-supported catalyst according to claim 2, wherein:
the molar ratio of the organic amine to the silver salt solution is (2-5) to 1;
the mass of the silver in the silver source solution is 0.1-0.7 wt% of that of the Raney copper catalyst;
the mass of the auxiliary agent in the silver source solution is 0-2 wt% of the Raney copper catalyst.
4. The method of preparing a silver-supported catalyst according to claim 1, wherein:
in step a, the preparation of the supported catalyst comprises:
under the condition of organic high polymer material forming and processing temperature or under the condition of uncured shaping, the die pressing is coated by the Raney alloy particles.
5. The method of preparing a silver-supported catalyst according to claim 4, wherein:
when the organic polymer material is thermoplastic, placing thermoplastic particles in the Raney alloy particles, or coating the Raney alloy particles on a thermoplastic sheet, and molding to obtain the supported catalyst.
6. The method of preparing a silver-supported catalyst according to claim 4, wherein:
when the organic polymer material is thermosetting plastic, firstly preparing a thermosetting plastic curing system;
adding Raney alloy powder into the mould, then adding a thermosetting plastic curing system, then adding the Raney alloy powder, and carrying out partial curing and shaping; then continuously carrying out mould pressing solidification on the partially solidified and shaped granular carrier coated with the Raney alloy powder to obtain a supported catalyst;
or,
and (3) molding the thermosetting plastic curing system into a sheet, incompletely curing, uniformly coating the Raney alloy powder on the upper surface and the lower surface, and continuously molding until the complete curing is achieved to obtain the supported catalyst.
7. The method of preparing a silver-supported catalyst according to claim 2, wherein:
the weight ratio of raney metallic copper to leachable elemental aluminum is 1: 1;
the soluble organic amine is one or more of triethanolamine, ethanolamine, ethylenediamine and hexamethylenediamine;
the soluble salt of silver is nitrate;
other soluble salt of the auxiliary agent is nitrate, chloride or acetate.
8. A silver supported catalyst prepared according to the process of any one of claims 1 to 7.
9. Use of a silver supported catalyst prepared according to the method of any one of claims 1 to 7 in the dehydrogenation of alkynes by carbon-tetra-hydrogenation.
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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
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
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
CN112657512A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Silver-fluorine supported catalyst, preparation method and application
CN112705219A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Multi-additive doped Raney copper catalyst, preparation method and application

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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
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
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
CN109456207A (en) * 2018-10-30 2019-03-12 昆山市祥和精细化工厂 The preparation method of 3- aminopropanol
CN109456207B (en) * 2018-10-30 2021-10-15 昆山市祥和精细化工厂 Preparation method of 3-aminopropanol
CN110385145A (en) * 2019-07-30 2019-10-29 厦门大学 A kind of preparation method of Pt/C catalyst, Pt/C catalyst and its application
CN112657512A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Silver-fluorine supported catalyst, preparation method and application
CN112657512B (en) * 2019-10-15 2024-07-02 中国石油化工股份有限公司 Silver-fluorine supported catalyst, preparation method and application
CN112705219A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Multi-additive doped Raney copper catalyst, preparation method and application

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Application publication date: 20180424