CN111085222A - Silver-zinc carbon raney copper catalyst and preparation method and application thereof - Google Patents
Silver-zinc carbon raney copper catalyst and preparation method and application thereof Download PDFInfo
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- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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Abstract
The invention relates to the field of catalysts for hydrogenation and alkyne removal in petrochemical industry, and discloses a preparation method of a silver-zinc carbon raney copper catalyst, which comprises the following steps: 1) uniformly mixing a metal active component with a carbonizable organic matter curing system, and then curing to obtain a catalyst precursor; 2) under the protection of inert gas, sequentially carrying out high-temperature carbonization and activation on the catalyst precursor to prepare a zinc-carbonized Raney copper catalyst, and adding water to prepare a catalyst suspension; 3) mixing soluble organic amine and silver salt to prepare silver source solution; 4) reacting the silver source solution with the catalyst suspension to prepare a silver-zinc carbon raney copper catalyst; wherein the metal active component comprises zinc, copper and aluminum. The silver-zinc carbon Raney copper catalyst is used for C4Distillate selective hydrogenation acetylene removal processIn the process, the method has the characteristics of high airspeed, high alkyne selection and low butadiene loss.
Description
Technical Field
The invention relates to the field of catalysts for hydrogenation and alkyne removal in petrochemical industry, in particular to a preparation method of a silver-zinc Raney copper carbide catalyst, the silver-zinc Raney copper carbide catalyst prepared by the method and the silver-zinc Raney copper carbide catalyst at C4Use of selective hydrogenation of fractions for alkyne removal.
Background
C4Distillate refers to a mixture of alkanes, alkenes, dienes and alkynes containing four carbon atoms, of which 1, 3-butadiene is an important chemical raw material for producing synthetic rubber. 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. To meet the requirements of the polymer grade, C needs to be added4The distillate is subjected to alkyne removal treatment.
The alkyne is industrially removed mainly by a two-stage solvent extractive distillation method, wherein butene, butane and the like are separated from crude butadiene by one-stage extraction, and alkyne (comprising Vinyl Acetylene (VA), Ethyl Acetylene (EA) and Methyl Acetylene (MA)) in the crude butadiene is removed by two-stage extraction. The process has the disadvantages of high energy consumption, high material loss, low process economy and the like.
In contrast, C is removed by selective hydrogenation4The alkyne in the distillate is a more economical alkyne removal method. The method utilizes a selective hydrogenation catalyst to carry out hydrogenation reaction on C4Acetylene hydrocarbons such as methylacetylene, ethylacetylene and vinylacetylene in the fraction are converted into butadiene, butene and a small amount of butane, and the method not only can effectively remove the acetylene hydrocarbons, but also can simplify the butadiene separation process. The alkyne removing method not only requires that alkyne can be effectively removed, but also needs to reduce the loss of 1, 3-butadiene as much as possible, so that the high selectivity of the catalyst is very important; in addition, high stability is also important for long-term, low-cost operation.
The catalyst with Cu as the main active component has high selectivity for selective hydrogenation and alkyne removal. US4440956A discloses a method for treating C4Copper-based catalyst for selective hydrogenation of alkynes for use in C4When selective hydrogenation is carried out, the loss of butadiene is less, the selectivity is good, but the catalyst has low space velocity and short service life, and needs to be regenerated frequently. 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.
CN103170349A discloses a mixed C4The selective hydrogenation copper catalyst comprises 5-50 wt% of active component Cu, 0.1-20 wt% of assistant metal and an alumina carrier, and organic amine is added in the preparation process of the catalyst to be complexed with the metal component, so that the uniformity and the dispersibility of an alloy formed on the surface of the catalyst are effectively improved, and the catalyst has better selectivity and stability compared with the prior art, but the problem of low-space-velocity operation cannot be solved.
US3912789A discloses a catalyst with Cu as active component and alumina as carrier, the selected assistant includes Ag, Pt, Pd, Mg, Ni, Co, Cr, Mo, etc., the catalyst has shorter active period and only has a service life of 175-200 h. In addition, the catalyst is only suitable for treating C with alkyne content of less than 0.2 wt%4And (6) cutting.
US4440956A disclosesA catalyst having an improved support, the catalyst being at C4Under the conditions of 300mL/h of feed, 4 of hydrogen-alkyne ratio, 2.8L/h of hydrogen flow and 60 ℃ of reaction temperature, the alkyne remained after selective hydrogenation is zero, the loss rate of 1, 3-butadiene can be controlled within 0.8 percent, but the catalyst can only process C with the alkyne content of less than 0.2 percent by weight4Cut and have a low space velocity.
In conclusion, a catalyst pair C with high space velocity and high selectivity was developed4The selective hydrogenation of the fractions for the removal of hydrocarbons is of great importance.
Disclosure of Invention
The object of the present invention is to overcome the existing C of the prior art4The preparation method of the silver-zinc carbonized raney copper catalyst and the silver-zinc carbonized raney copper catalyst prepared by the method have the defects of low catalyst airspeed, low alkyne selectivity and high butadiene loss in the selective hydrogenation alkyne removal process of fractions. The silver-zinc carbon Raney copper catalyst is used for C4In the process of selective hydrogenation and alkyne removal of the fraction, the method has the characteristics of high space velocity, high alkyne selection and low butadiene loss.
The inventor of the invention discovers in research that the silver-zinc carbon raney copper catalyst can be prepared by dripping a silver source solution prepared by mixing soluble organic amine and silver salt into a suspension of the zinc carbon raney copper catalyst prepared by high-temperature carbonization and activation. The silver-zinc carbon Raney copper catalyst is applied to high airspeed C4When the acetylene is removed by fraction selective hydrogenation, the vinyl acetylene can be removed in a targeted manner, namely, the selectivity to the vinyl acetylene is higher (the residual vinyl acetylene is less than 8ppm), and the loss amount of butadiene is low (less than 0.3 weight percent).
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a silver-zinc raney copper carbide catalyst, comprising the steps of:
1) uniformly mixing a metal active component with a carbonizable organic matter curing system, and then curing to obtain a catalyst precursor;
2) under the protection of inert gas, sequentially carrying out high-temperature carbonization and activation on the catalyst precursor to prepare a zinc-carbonized Raney copper catalyst, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) reacting the silver source solution with the catalyst suspension to prepare a silver-zinc carbon raney copper catalyst;
wherein the metal active component comprises zinc, copper and aluminum;
the carbonizable organic curing system includes a carbonizable organic and an additive.
In a second aspect, the present invention provides a silver-zinc raney copper carbide catalyst prepared by the method of the first aspect of the present invention.
In a third aspect, the invention provides a silver-zinc Raney copper carbide catalyst as described in the invention at C4Use of selective hydrogenation of fractions for alkyne removal.
By adopting the technical scheme, the silver-zinc carbon raney copper catalyst provided by the invention is used for C4In the process of selective hydrogenation and alkyne removal of the fraction, the method has the characteristics of high space velocity, high alkyne selection and low butadiene loss.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a silver-zinc Raney copper carbide catalyst, which comprises the following steps:
1) uniformly mixing a metal active component with a carbonizable organic matter curing system, and then curing to obtain a catalyst precursor;
2) under the protection of inert gas, sequentially carrying out high-temperature carbonization and activation on the catalyst precursor to prepare a zinc-carbonized Raney copper catalyst, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) reacting the silver source solution with the catalyst suspension to prepare a silver-zinc carbon raney copper catalyst;
wherein the metal active component comprises zinc, copper and aluminum;
the carbonizable organic curing system includes a carbonizable organic and an additive.
Preferably, the weight ratio of the metal active component to the carbonizable organic curing system is (0.01-99): 1;
based on the total weight of the metal active components, the content of zinc is 0.01-20 wt%, the content of copper is 10-50 wt%, and the content of aluminum is 40-80 wt%;
the silver source solution is used in an amount such that the weight ratio of the silver to the zinc-carbon raney copper catalyst is (0.01-1.0): 100.
in order to further improve the selectivity of the silver-zinc Raney copper carbide catalyst prepared by the method of the invention to alkyne, namely the selectivity of vinyl acetylene, preferably, the silver source solution is used in such an amount that the weight ratio of the silver to the zinc Raney copper carbide catalyst is (0.1-0.6): 100.
in the present invention, the carbonizable organic substance 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 the present invention, the organic substance that can be carbonized is not particularly limited, and may be any organic substance that satisfies the above-described conditions, and the organic substance that can be carbonized may be an organic polymer compound. Preferably, the organic matter capable of being carbonized is at least one selected from epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, starch, viscose, lignin, cellulose, styrene-butadiene rubber and polyurethane rubber.
In the present invention, the selection of the additive is not particularly limited. Preferably, the additive is selected from at least one of curing agents, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, anti-drip agents, anti-blocking agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents. 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 the method of the present invention, it is preferable that the solidification system is in a liquid state or a powder state.
According to the method of the present invention, in step 1), there is no particular requirement for the specific operation method of the curing, and the method of the present invention preferably comprises the following specific operation steps of the curing: and mixing the metal active component containing copper, aluminum and zinc with a curing system to obtain a mixed material, and then introducing the mixed material into a mold for tabletting and molding. As an embodiment of the present invention, the curing may be performed by the following method: mixing the mixture of copper, aluminum and zinc with a curing system to obtain a mixed material, then putting the mixed material into a die, and carrying out die pressing on a tablet press to form a sheet with a proper thickness; heating the tablet press to a proper temperature, putting the formed sheet into the die again, and curing under a certain pressure on the tablet press; the cured sheet is cut into small particles.
According to the method of the invention, in the step 1), the obtained catalyst precursor can be processed into particles which can be used in a fixed bed or fluidized bed reactor by cutting, stamping or crushing and the like by using any available organic polymer material processing equipment, the particle size of the particles is based on the size of the particles which can meet the requirement of the fixed bed catalyst or 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 above shapes, and the like, preferably sphere, ring, tooth shape, cylinder or the combination of the above shapes.
In the present invention, the high-temperature carbonization may be performed in a high-temperature electric furnace, and in the present invention, it is preferable that the inert gas includes nitrogen and/or argon, and the carbonization may be performed in a reducing atmosphere such as hydrogen.
In the present invention, preferably, the high temperature carbonization conditions include: the carbonization temperature is 400-; more preferably, the carbonization temperature is 600-950 ℃, and the carbonization time is 2-6 h.
In the present invention, preferably, the activation is carried out in a lye, the concentration of which is 2 to 40% by weight; more preferably 5 to 20 wt%.
In the present invention, the alkali solution is preferably an aqueous sodium hydroxide solution and/or an aqueous potassium hydroxide solution, and more preferably an aqueous sodium hydroxide solution.
In the present invention, preferably, the activation conditions include: the activation temperature is 20-100 ℃, and the activation time is 0.5-3 h.
In the present invention, it is preferable that the zinc-carbon raney copper catalyst has an average particle diameter of 2 to 3 mm.
In the present invention, the solvent used in the preparation of the catalyst suspension by adding the solvent to the zinc-carbon raney copper catalyst is not particularly limited, and may be any of various solvents known in the art for preserving raney copper catalyst.
According to the invention, 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 carbonized catalyst precursor is activated by alkali liquor 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.
In the invention, the preparation process of the silver source solution comprises the following steps: the soluble organic amine is mixed with a silver salt, preferably silver nitrate. As a specific embodiment of the present invention, the following method may be adopted: adding a certain amount of silver nitrate into a certain amount of water, and stirring until the silver nitrate is dissolved; then, a certain amount of organic amine is dripped into a certain amount of water; and (3) dropwise adding the organic amine solution into a silver nitrate solution to form a transparent and uniform solution, and then carrying out constant volume to obtain a silver source solution.
Preferably, the concentration of silver in the silver source solution is 0.05-20mgAg/mL, more preferably 1-6 mgAg/mL.
In the present invention, preferably, the molar ratio of the organic amine to silver is (1-10): 1, preferably (2-5): 1.
in the present invention, the organic amine is not particularly limited and may be any of various organic amines capable of forming a complex with metallic silver, and preferably, the organic amine is at least one selected from the group consisting of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, ethylenediamine, dodecylamine, triethylenediamine, cyclohexylamine, and hexamethylenetetramine; more preferably at least one of isopropylamine, triethanolamine and hexamethylenediamine.
In the invention, preferably, the silver source solution is dropwise added into the catalyst suspension to react for 1-2h, and the silver-zinc Raney copper carbide catalyst is prepared after filtration and washing.
In a second aspect, the present invention provides a silver-zinc raney copper carbide catalyst prepared by the method of the first aspect of the present invention.
In a third aspect, the invention provides a silver-zinc Raney copper carbide catalyst as described in the invention at C4Use of selective hydrogenation of fractions for alkyne removal.
Preferably, said C4The reaction conditions for the selective hydrogenation of the distillate to remove acetylene include: the temperature of a reaction inlet is 30-60 ℃, the reaction pressure is 0.5-2.0MPa, and C is used4The reaction space velocity of liquid volume measurement in the fraction is 2-20h-1Hydrogen and C4The molar ratio of alkynes in the fraction is (0.2-10): 1. with C4The alkyne content is 0.6-1.5 wt% based on the total weight of the fraction. More preferably, with C4The reaction space velocity of liquid volume measurement in the fraction is 10-20h-1。
Preferably, said C4The distillate selective hydrogenation alkyne removal reaction is carried out in a fixed bed reactor.
The essential difference between the present invention and the prior art is mainly that:
in the preparation method for preparing the Raney copper catalyst by taking metal powder as a precursor through carbonization, the preparation and the forming of the catalyst are completed in one step, and the preparation method is a preparation method of a novel catalytic material. The method can be used for preparing the composite Raney copper catalyst doped with various metal powders in one step, and can also solve the problem that the alloy obtained after doping certain metals is powdery and cannot be applied to a fixed bed reactor.
The invention has the beneficial effects that:
the zinc-silver doped Raney copper catalyst provided by the invention is used for high space velocity and C4When the fraction is in the acetylene removing process by selective hydrogenation, the selectivity is high, the residual vinyl acetylene after the reaction is less than 8ppm, and the loss of butadiene is less than 0.3 weight percent.
The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, various raw materials used are commercially available.
Preparation example 1
(1) Fully mixing 200g of powdery phenolic resin and 24g of curing agent hexamethylenetetramine by using a high-speed stirrer to obtain 224g of mixture;
(2) fully mixing 100g of the mixture, 545g of copper powder, 468g of aluminum powder and 100g of zinc powder by using a high-speed stirrer; 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 small particles to obtain a catalyst precursor;
(3) measuring 200mL of the small particles obtained in the step (2), carbonizing the small particles in a tubular high-temperature electric furnace, wherein the heating rate is 10 ℃/min, the furnace temperature is 650 ℃, keeping the temperature for 3h, and the flow is 200mL/min under the protection of nitrogen;
(4) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the zinc-carbon Raney's copper catalyst, adding water to prepare a catalyst suspension, and storing for later use.
(5) Preparing a silver source solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(6) And (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 2
(1) Fully mixing 200g of powdery phenolic resin and 24g of curing agent hexamethylenetetramine by using a high-speed stirrer to obtain 224g of mixture;
(2) fully mixing 100g of the mixture, 545g of copper powder, 468g of aluminum powder and 50g of zinc powder by using a high-speed stirrer; heating a tablet machine to 100 ℃, 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 140 ℃, putting the formed sheet into the die again, and curing for 12min under the pressure of 5MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into small particles to obtain a catalyst precursor;
(3) measuring 200mL of the small particles obtained in the step (2), carbonizing the small particles in a tubular high-temperature electric furnace, wherein the heating rate is 10 ℃/min, the furnace temperature is 650 ℃, keeping the temperature for 3h, and the flow is 200mL/min under the protection of nitrogen;
(4) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), filtering the solution after 3.5 hours, washing the solution until the solution is nearly neutral to obtain a zinc-carbon Raney's copper catalyst, adding water to prepare a catalyst suspension, and storing the suspension for later use;
(5) 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, and dropwise adding 1.9mL of triethanolamine solution (density: 1.1g/mL of triethanolamine) into 10mL of deionized water to prepare a uniform solution. The molar ratio of triethanolamine 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.
(6) And (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 3
(1) Fully mixing 200g of powdery phenolic resin and 24g of curing agent hexamethylenetetramine by using a high-speed stirrer to obtain 224g of mixture;
(2) fully mixing 100g of the mixture, 545g of copper powder, 468g of aluminum powder and 200g of zinc powder by using a high-speed stirrer; heating a tablet machine to 110 ℃, 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 120 ℃, putting the formed sheet into the die again, and curing for 20min under the pressure of 4MPa on the tablet press; cutting the cured sheet with the thickness of 2mm into small particles to obtain a catalyst precursor;
(3) measuring 200mL of the small particles obtained in the step (2), carbonizing the small particles in a tubular high-temperature electric furnace, wherein the heating rate is 10 ℃/min, the furnace temperature is 900 ℃, keeping the temperature for 2h, and the flow is 200mL/min under the protection of nitrogen;
(4) preparing 500mL of 10 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain a zinc-carbon raney copper catalyst, adding water to prepare a catalyst suspension, and storing for later use;
(5) preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(6) And (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 4
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
and (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 20mL (the content of silver is 60mg and accounts for 0.4 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 5
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
and (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 30mL (the content of silver is 90mg and accounts for 0.6 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 6
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
and (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 0.5mL (the content of silver is 1.5mg, and accounts for 0.01 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 7
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
and (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 50mL of the silver source solution (the content of silver is 150mg, and accounts for 1 wt% of the mass of the added catalyst) obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver-zinc carbonized raney copper catalyst.
Preparation example 8
The process of example 1 is followed except that step (5) is carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver is 2: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
Preparation example 9
The process of preparation example 1 was followed except that step (5) was carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver was 10: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
Comparative preparation example 1
(1) Fully mixing 200g of powdery phenolic resin and 24g of curing agent hexamethylenetetramine by using a high-speed stirrer to obtain 224g of mixture;
(2) fully mixing 100g of the mixture, 545g of copper powder, 468g of aluminum powder and 100g of zinc powder by using a high-speed stirrer; 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 small particles to obtain a catalyst precursor;
(3) measuring 200mL of the small particles obtained in the step (2), carbonizing the small particles in a tubular high-temperature electric furnace, wherein the heating rate is 10 ℃/min, the furnace temperature is 650 ℃, keeping the temperature for 3h, and the flow is 200mL/min under the protection of nitrogen;
(4) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the zinc-carbon Raney's copper catalyst, adding water to prepare a catalyst suspension, and storing for later use.
Comparative preparation example 2
(1) Fully mixing 200g of powdery phenolic resin and 24g of curing agent hexamethylenetetramine by using a high-speed stirrer to obtain 224g of mixture;
(2) fully mixing 100g of the mixture, 545g of copper powder and 468g of aluminum powder by using a high-speed stirrer; 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 small particles to obtain a catalyst precursor;
(3) measuring 200mL of the small particles obtained in the step (2), carbonizing the small particles in a tubular high-temperature electric furnace, wherein the heating rate is 10 ℃/min, the furnace temperature is 650 ℃, keeping the temperature for 3h, and the flow is 200mL/min under the protection of nitrogen;
(4) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the Raney's copper carbide catalyst, adding water to prepare a catalyst suspension, and storing for later use.
(5) Preparing a silver source solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(6) And (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver carbonized raney copper catalyst.
Example 1
45mL of the catalyst obtained in production examples 1 to 9 and comparative production examples 1 to 2 was charged in a fixed bed reactor, and after replacement with nitrogen, hydrogen and C were added4The molar ratio of alkynes in the fraction was 5: 1 is passed into the reactor. C4The compositions (mass percentages) of the fractions are shown in Table 1. The reaction conditions are as follows:
at an inlet temperature of 45 ℃ and a reaction pressure of 1.5MPa, and C4The space velocity of the reaction measured by the volume of the liquid in the fraction is 10h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions.
Determination of C by gas chromatography4The contents of the components in the fractions.
For the above catalyst C4The selective hydrogenation catalytic performance of the fractions was evaluated, and the amounts of residual vinylacetylene and butadiene lost after the reaction was continued for 100 hours are shown in Table 2.
TABLE 1
| Components | Content (wt%) |
| Isobutane | 2.35 |
| N-butane | 4.73 |
| Trans-2-butene | 4.49 |
| 1-butene | 13.9 |
| Isobutene | 21.31 |
| Cis-2-butene | 3.36 |
| 1, 2-butadiene | 0.17 |
| 1, 3-butadiene | 48.56 |
| Methylacetylene | 0.08 |
| Ethyl acetylene | 0.73 |
| Vinyl acetylene | 0.14 |
TABLE 2
| Catalyst sample | Residual vinyl acetylene (ppm) | Butadiene loss amount (% by weight) |
| Preparation example 1 | 4.2 | 0.18 |
| Preparation example 2 | 3.9 | 0.20 |
| Preparation example 3 | 4.6 | 0.19 |
| Preparation example 4 | 4.3 | 0.22 |
| Preparation example 5 | 5.2 | 0.21 |
| Preparation example 6 | 7.5 | 0.30 |
| Preparation example 7 | 8.0 | 0.27 |
| Preparation example 8 | 5.7 | 0.21 |
| Preparation example 9 | 7.3 | 0.28 |
| Comparative preparation example 1 | 20 | 0.7 |
| Comparative preparation example 2 | 54 | 1.2 |
Example 2
The process of example 1 was followed except that the reaction conditions were:
at an inlet temperature of 45 ℃ and a reaction pressure of 1.5MPa, and C4The reaction space velocity of liquid volume measurement in the fraction is 15h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions. The results are shown in Table 3.
TABLE 3
Example 3
The process of example 1 was followed except that the reaction conditions were:
at an inlet temperature of 45 ℃ and a reaction pressure of 1.5MPa, and C4The reaction space velocity of the liquid volume metering in the fraction is 20h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions. The results are shown in Table 4.
TABLE 4
| Catalyst sample | Residual vinyl acetylene (ppm) | Butadiene loss amount (% by weight) |
| Preparation example 1 | 7.2 | 0.19 |
| Preparation example 2 | 7.3 | 0.20 |
| Preparation example 3 | 6.9 | 0.19 |
| Preparation example 4 | 7.3 | 0.22 |
| Preparation example 5 | 7.1 | 0.25 |
| Preparation example 6 | 7.9 | 0.30 |
| Preparation example 7 | 8.0 | 0.28 |
| Preparation example 8 | 7.4 | 0.21 |
| Preparation example 9 | 8.0 | 0.29 |
| Comparative preparation example 1 | 30 | 0.7 |
| Comparative preparation example 2 | 70 | 1.3 |
As can be seen from the results in tables 2 to 4, the silver-zinc Raney copper carbide catalyst prepared by the method of the invention is applied to C4When the fraction is in the process of removing alkyne by hydrogenation, the time is 10 to 20 hours-1Can remove the vinyl acetylene in a targeted way at a high space velocity, has higher selectivity to the vinyl acetylene (the residual vinyl acetylene is less than 8ppm), and simultaneously has the loss amount of butadieneLow (less than 0.3 wt%).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A preparation method of a silver-zinc Raney copper carbide catalyst comprises the following steps:
1) uniformly mixing a metal active component with a carbonizable organic matter curing system, and then curing to obtain a catalyst precursor;
2) under the protection of inert gas, sequentially carrying out high-temperature carbonization and activation on the catalyst precursor to prepare a zinc-carbonized Raney copper catalyst, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) reacting the silver source solution with the catalyst suspension to prepare a silver-zinc carbon raney copper catalyst;
wherein the metal active component comprises zinc, copper and aluminum;
the carbonizable organic curing system includes a carbonizable organic and an additive.
2. The method of claim 1, wherein the weight ratio of the metal active component to the carbonizable organic cure system is (0.01-99): 1;
based on the total weight of the metal active components, the content of zinc is 0.01-20 wt%, the content of copper is 10-50 wt%, and the content of aluminum is 40-80 wt%;
the silver source solution is used in an amount such that the weight ratio of the silver to the zinc-carbon raney copper catalyst is (0.01-1.0): 100, preferably (0.1-0.6): 100.
3. the method according to claim 1 or 2, wherein in step 2), the high temperature carbonization conditions comprise: the carbonization temperature is 400-1200 ℃, and the carbonization time is 1-10 h.
4. The process according to claim 1 or 2, wherein in step 2), the activation is carried out in a lye, the lye having a concentration of 2-40% by weight;
preferably, the activation conditions include: the activation temperature is 20-100 ℃, and the activation time is 0.5-3 h.
5. The process of claim 1 or 2, wherein the zinc-carbon raney copper catalyst has an average particle size of 2-3 mm.
6. The method according to claim 1 or 2, wherein in the silver source solution, the concentration of silver is 0.05-20mgAg/mL, preferably 1-6 mgAg/mL;
preferably, the molar ratio of the organic amine to silver is (1-10): 1, preferably (2-5): 1.
7. the method according to any one of claims 1 to 6, wherein the organic amine is selected from at least one of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, ethylenediamine, dodecylamine, triethylenediamine, cyclohexylamine, and hexamethylenetetramine;
preferably at least one of isopropylamine, triethanolamine and hexamethylenediamine.
8. The method according to any one of claims 1 to 6, wherein the carbonizable organic substance is selected from at least one of epoxy resin, phenol resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, starch, viscose fiber, lignin, cellulose, styrene-butadiene rubber, urethane rubber;
the additive is selected from at least one of curing accelerator, dye, pigment, colorant, antioxidant, stabilizer, plasticizer, lubricant, flow modifier or auxiliary agent, flame retardant, anti-dripping agent, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modifier, demolding auxiliary agent and nucleating agent.
9. A silver-zinc raney copper carbide catalyst prepared according to the process of any one of claims 1 to 8.
10. The silver-zinc Raney copper carbide catalyst of claim 9 at C4Use of selective hydrogenation of fractions for alkyne removal.
11. Use according to claim 10, wherein C is4The reaction conditions for the selective hydrogenation of the distillate to remove acetylene include: the temperature of a reaction inlet is 30-60 ℃, the reaction pressure is 0.5-2.0MPa, and C is used4The reaction space velocity of liquid volume measurement in the fraction is 2-20h-1Hydrogen and C4The molar ratio of alkynes in the fraction is (0.2-10): 1. with C4The alkyne content is 0.6-1.5 wt% based on the total weight of the fraction.
12. Use according to claim 11, wherein C is4The reaction space velocity of liquid volume measurement in the fraction is 10-20h-1。
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