CN107952450A - A kind of preparation method, catalyst and the application of silver carbonization raney copper catalyst - Google Patents
A kind of preparation method, catalyst and the application of silver carbonization raney copper catalyst Download PDFInfo
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- CN107952450A CN107952450A CN201610899111.XA CN201610899111A CN107952450A CN 107952450 A CN107952450 A CN 107952450A CN 201610899111 A CN201610899111 A CN 201610899111A CN 107952450 A CN107952450 A CN 107952450A
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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
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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Abstract
The invention discloses a kind of preparation method, catalyst and the application of silver carbonization raney copper catalyst.Method includes：(1) Raney alloy particle is uniformly mixed with the curing system for the organic matter that can be carbonized, then cures, obtain catalyst precarsor；(2) under inert gas shielding, high temperature cabonization catalyst precarsor obtained above, then activated to obtain carbonization raney copper catalyst；(3) 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；(4) carbonization raney copper catalyst is added in deionized water and aaerosol solution is formed by stirring, silver-colored source solution in above-mentioned steps (3) is added dropwise in carbonization raney copper catalyst solution, silver carbonization raney copper catalyst is made after reaction 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
Technical field
The present invention relates to carbon four to select acetylene hydrogenation catalyst field, further says, is to be related to a kind of silver carbonization thunder Buddhist nun
Preparation method, catalyst and the application of copper catalyst.
Background technology
1,3-butadiene is a kind of important industrial chemicals for producing synthetic rubber, about contains 40 in cracking mixing carbon four
~50% 1,3-butadiene, is the main source of butadiene.Requirement of the polymer grade alkadienes to alkyne impurities is very high, such as polymerize
Level butadiene requires purity to be more than 99.7%, and alkynes content is less than 50ppm.In order to meet the requirement of polymer grade, it is necessary to carbon four
Fraction is carried out except alkynes is handled.At present, the separation butadiene from mixing carbon four industrially used mainly uses two sections of solvent extractions
The technique of rectifying, wherein one section separates butylene, butane etc. and crude butadiene, two sections by alkynes (including the second in crude butadiene
Vinyl acetylene (VA), ethyl acetylene (MA) and allylene (MA)) remove, afterwards polymer grade can be obtained by rectifying purifying again
The shortcomings that butadiene, the technique is high energy consumption, loss of material is more, process economics are low.
The alkynes that selective hydrogenation removes in C-4-fraction is a kind of more economical to remove alkynes method.This method is added using selection
The alkynes such as the allylene in c4 fraction, ethyl acetylene, vinylacetylene are converted into fourth by hydrogen catalyst by hydrogenation reaction
Diene, butylene and a small amount of butane, this method not only can effectively remove alkynes, can also simplify separate butadiene flow.
It is this effectively to remove alkynes except alkynes method does not require nothing more than, also to reduce the loss of 1,3-butadiene to the greatest extent, therefore to catalyst
Selectivity requires very high；In addition, in order to achieve the purpose that long-term, low cost operation, high stability is also particularly significant.
Copper-based catalysts are to selective hydrogenation except alkynes has very high selectivity, and patent US4440956 is pointed out, cupper-based catalyst
Agent is used for the selection acetylene hydrogenation of carbon four on the premise of index is removed, and the loss of butadiene is lacked, and selectivity is good, but air speed is low, the longevity
Order short, it is necessary to frequent regeneration.Catalyst is copper catalyst used by the KLP technologies of industrialized U.S. DOW companies,
The whole world, which is built together, ten covering devices, and there is also the problems such as regeneration is frequent, and air speed is relatively low for catalyst used by KLP technologies.To the greatest extent
Pipe has many documents and patent, and such as patent CN103170349, the addition that US3912789A is related to promoter metal can improve catalysis
The selectivity and stability of agent, but catalyst air speed it is low the problem of still fail to change.Therefore develop a kind of while there is height
The Cu catalyst of air speed and high selectivity selects the application value of hydrogen addition technology very great in carbon four.
The content of the invention
To solve produced problem in the prior art, the present invention provides a kind of preparation side of silver carbonization raney copper catalyst
Method, catalyst and application.The catalyst of the present invention can be 30 DEG C~60 DEG C in reaction inlet temperature, reaction pressure be 0.5~
2.0MPa, using the reaction velocity of the liquid volume metering of c4 fraction as 2~20h-1, hydrogen and alkynes volume ratio for 0.2~
Under conditions of 10mol/mol, alkynes in liquid phase c4 fraction is removed to below 30ppm, the control of 1,3-butadiene loss late exists
Less than 3%.
An object of the present invention is to provide a kind of preparation method of silver carbonization raney copper catalyst.
Including：
(1) Raney alloy particle is uniformly mixed with the curing system for the organic matter that can be carbonized, then cures, be catalyzed
Agent precursor；The weight ratio of Raney alloy particle and the organic matter curing system that can be carbonized is 1：99~99：1；Preferably 10：90~
90：10；More preferably 25：75~75：25；
The curing system for the organic matter that can be carbonized includes the organic matter and additive that can be carbonized；
(2) under inert gas shielding, high temperature cabonization catalyst precarsor obtained above, then activated to obtain carbonization thunder
Buddhist nun's copper catalyst；
The raney copper catalyst grain diameter that is carbonized is 2~3mm.
The preparation method of conventional raney copper catalyst can be used, in of the invention, is preferably carried out according to the following steps：Causticity
Alkali is preferably NaOH, and the concentration of caustic-alkali aqueous solution is 2~40wt%, preferably 5~20wt%, and extraction temperature is 20~100 DEG C,
Extraction times are 0.5~3h, and the dosage of caustic alkali is 1~3 times, preferably 1~2 times of alloy mass.
(3) soluble organic amine and water are made into mixed solution, are redissolved soluble silver salt and the solubility of other auxiliary agents
Salt, is prepared into silver-colored source solution；
The molar ratio of organic amine and silver salt solution is 1：1~10:1；Preferably 2：1~5：1；
The molar ratio of organic amine and auxiliary agent is 1：2~10:1,
Other auxiliary agents include Co, Fe, Mn, Ni, Zn, the one or more in Cr, Pd；
It is described solubility organic amine for ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine,
Isopropylamine, diethylamine, aniline, N, in accelerine, lauryl amine, triethylene diamine, cyclohexylamine and six tetramethyl urotropines
One or more；The one or more of preferably triethanolamine, monoethanolamine, ethylenediamine and hexamethylene diamine；
(4) carbonization raney copper catalyst is added in deionized water and aaerosol solution is formed by stirring, by above-mentioned step
Suddenly the silver-colored source solution in (3) is added dropwise in carbonization raney copper catalyst solution, and silver carbon is made when reaction 1~2 is small, after washing
Change raney copper catalyst；
Silver-colored quality is 0.01w%~1.0wt% of carbonization raney copper catalyst in silver-colored source solution；Preferably 0.1wt%
~0.6wt%；
The quality of promoter metal is 0~5wt% of carbonization raney copper catalyst in silver-colored source solution, preferably 0.1%~
1.0wt%；
The organic matter that can be carbonized refers to：Handle organic matter under certain temperature, atmospheric condition, hydrogen, oxygen in organic matter,
Nitrogen, sulphur etc. completely or partially vapor away, so as to obtain a kind of very high synthetic material of phosphorus content, obtained carbon material has resistance to
The performance such as high temperature, high intensity, high-modulus, porous；The organic matter being carbonized is organic high molecular compound；
The organic high molecular compound that can be carbonized is preferably：Epoxy resin, phenolic resin, furane resins, polystyrene, benzene
Ethene-divinylbenzene copolymer, polyacrylonitrile, starch, viscose rayon, lignin, cellulose, butadiene-styrene rubber, polyurethane rubber
At least one of；
In the gap of carbon, porous carbon structure effectively scatter Raney alloy particle Raney alloy particle distribution
Come, Raney alloy particle is reduced sintering as far as possible during pyroreaction, effectively raise the use of catalyst
Service life.In addition solution or gas can easily touch Raney alloy, composite catalyst be soaked with lye, thunder Buddhist nun
Alloy particle obtains activation and forms porous high activity Raney metal, while a small amount of agraphitic carbon is also washed away, continuous phase carbon
Material is able to reaming, and more Raney alloys are exposed, so that catalyst has very high activity.
The additive can use the common additive in this area, such as：It is curing accelerator, dyestuff, pigment, colouring agent, anti-
Oxidant, stabilizer, plasticizer, lubricant, flow ability modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, lead
One kind or combination in electric agent, polyvalent metal ion, impact modifying agent, demolding aids, nucleator.Additive therefor dosage is
Conventional amount used, or be adjusted according to the requirement of actual conditions.
Wherein,
Carburizing temperature is 400~1200 DEG C in step (2)；It is preferred that 600~950 DEG C, protective gas is nitrogen or argon gas
Deng inert gas, when carbonization 1~6 is small.
In step (3), silver-colored soluble-salt is nitrate, and other promoter soluble salts are nitrate, chloride or second
Hydrochlorate.
Raney alloy includes metallic copper and metallic aluminium.
The second object of the present invention is to provide silver carbonization raney copper catalyst prepared by a kind of method.
The third object of the present invention is to provide silver carbonization raney copper catalyst prepared by a kind of method and adds in carbon four
Hydrogen removes the application in alkynes.
Reaction inlet temperature be 30 DEG C~60 DEG C, reaction pressure is 0.5~2.0MPa, the liquid volume with c4 fraction
The reaction velocity of metering is 2~20h-1, under conditions of hydrogen and alkynes volume ratio be 0.2~10mol/mol, by liquid phase c4 fraction
Middle alkynes is removed to below 30ppm, and 1,3-butadiene loss late is controlled below 3%
The present invention preparation method technical solution be：
(1) composite catalyst of the present invention is by comprising the following steps preparation：
A, curing system is often prepared with curing formula according to the organic matter that can be carbonized, curing system is liquid or powder
Shape；
B, Raney alloy particle is uniformly mixed with the curing system for the organic matter that can be carbonized, then cures, be catalyzed
Agent precursor；
C, under inert gas shielding, high temperature cabonization catalyst precarsor obtained above, lives again after catalyst is made
Change obtains carbonization raney copper catalyst.
(2) soluble organic amine and water are made into mixed solution, are redissolved soluble silver salt and the solubility of other auxiliary agents
Salt, other auxiliary agents include Co, Fe, Mn, Ni, Zn, and the one or more in Cr, Pd, are prepared into silver-colored source solution.
(3) carbonization raney copper catalyst is added in deionized water and aaerosol solution is formed by stirring, by above-mentioned step
Suddenly the silver-colored source solution in (2) is added dropwise in carbonization raney copper catalyst solution, without adjusting pH value, without any reduction
Agent, reaction 1~2 it is small when after take out catalyst be washed with deionized three times after it is stand-by.
It is preferred that：
In step (1), the organic matter that can be carbonized refers to：Organic matter, organic matter are handled under certain temperature, atmospheric condition
In hydrogen, oxygen, nitrogen, sulphur etc. is all or part of vapors away, so as to obtain a kind of very high synthetic material of phosphorus content, obtained carbon
Material has the performance such as high temperature resistant, high intensity, high-modulus, porous.
In step a, it is often to use curing formula according to the organic matter that can be carbonized to prepare curing system, and when preparation can add
Optional one or more are selected from following additive：Curing accelerator, dyestuff, pigment, colouring agent, antioxidant, stabilizer,
Plasticizer, lubricant, flow ability modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal
Ion, impact modifying agent, demolding aids, nucleator etc..Additive therefor dosage is conventional amount used, or according to actual conditions
It is required that it is adjusted.The curing system of preparation is liquid system or powdery system, and liquid system can be stirred evenly directly；Powdery is consolidated
State system can directly be blended uniformly；It is equal that granulated solid system can use industrial common any disintegrating apparatus to be blended after crushing
It is even.
In stepb, the weight ratio of the Raney alloy particle and the organic matter curing system that can be carbonized is 1：99~
99：1, it is preferably 10：90~90：10, more preferably 25：75~75：25.Obtained catalyst precarsor can use any available
High-molecular organic material process equipment, by cutting, cutting, punching press or it is broken the methods of be processed into fixed bed or fluid bed
React the particle that can use, the particle size of particle is can meet needed for fixed bed catalyst or fluid catalyst
On the basis of particle size, the shape of particle can be any irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical
Body, prism-shaped body, cube, cuboid, ring bodies, half-annuli, hollow cylinder, tooth form or more combination of shape etc.,
It is preferred that the combination of spherical, annular, tooth form, cylinder or more shape.
Carbonization described in step c carries out generally in tubular heater, and carbonization operation temperature is generally 400~1900 DEG C,
It is preferred that 600~950 DEG C, protective gas is the inert gases such as nitrogen or argon gas, when carbonization 1~12 is small.For example, phenolic resin exists
When 850 DEG C of carbonizations 3 are small, you can carbonization, forms porous carbon.Higher carburizing temperature can cause the carbon obtained after carbonization more
Add regular.
Activation process in step c, carbonization raney copper catalyst is without fixed mesh number limitation, preferably 2~3mm.Caustic alkali is excellent
Elect NaOH as, the concentration of caustic-alkali aqueous solution is 2~40wt%, preferably 5~20wt%, and extraction temperature is 20~100 DEG C, extracting
Time is 0.5~3h, and the dosage of caustic alkali is 1~3 times, preferably 1~2 times of alloy mass.It is preferred that with 20~50 DEG C go from
Raney copper catalyst to washing lotion pH value after sub- water washing extracting is 7~9, and the catalyst finally obtained is stored in deionization
In water or absolute ethyl alcohol.
In step (2), silver-colored soluble-salt is nitrate, and silver-colored quality is urged to add carbonization Lei Nitong in silver-colored source solution
0.05~2.0wt% of agent quality.Other promoter soluble salts are that its total content such as nitrate, chloride or acetate is
0-5%, preferably 0.1~2.0%.Soluble organic amine is ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, second two
Amine, butylamine, isopropylamine, aniline, N, in accelerine, lauryl amine, triethylene diamine, cyclohexylamine and six tetramethyl urotropines
One or more, preferably triethanolamine, monoethanolamine, the one or more of ethylenediamine and hexamethylene diamine.
In step (3), silver carbonization raney copper catalyst is that silver-colored source solution is supported on carbonization thunder Buddhist nun using displacement reaction
Copper catalyst surface.Carbonization raney copper catalyst includes continuous phase carbon and dispersed phase Raney alloy particle, wherein dispersed phase thunder Buddhist nun
Alloy particle is evenly or uniformly dispersed in continuous phase carbon, and the continuous phase carbon is organic matter by that can be carbonized or it is mixed
Obtained after compound carbonization；The Raney alloy includes metallic copper and the element aluminum that can be leached.
The present invention application process technical solution be：
Be carbonized raney copper catalyst using silver, reaction inlet temperature be 30 DEG C~60 DEG C, reaction pressure be 0.5~
2.0MPa, using the reaction velocity of the liquid volume metering of c4 fraction as 2~20h-1, hydrogen and alkynes volume ratio for 0.2~
Under conditions of 10mol/mol, alkynes in liquid phase c4 fraction is removed to below 30ppm, the control of 1,3-butadiene loss late exists
Less than 3%
The present invention and the essential distinction of the prior art be,
(1) the copper catalyst reaction velocity of alumina load it is low (<6h-1), the catalyst that the present invention uses can be in high-altitude
(air speed under speed>10h-1) the selection acetylene hydrogenation reaction of carbon four, and 1 are carried out, the loss late of 3 butadiene is relatively low.
(2) in the gap of carbon, porous carbon structure effectively disperses Raney alloy particle Raney alloy particle distribution
Come, Raney alloy particle is reduced sintering as far as possible during pyroreaction, effectively raise making for catalyst
Use the service life.And carbonization raney copper catalyst makes its density smaller due to its loose shape structure.The carbonization Lei Nitong of same volume is urged
Agent quality is much smaller than the quality of raney copper catalyst.
(3) the silver carbonization raney copper catalyst that organic amine is prepared as complexing agent, avoids by the use of nitrate and is used as silver-colored source
Hydrolysis problem, can accurately control silver in the content on carbonization thunder Buddhist nun's copper surface, and improve point of the silver on carbonization thunder Buddhist nun's copper surface
Divergence.
(4) silver-organic amine complex reduces usage amount silver-colored in reaction, play it is cost-effective, it is efficient the features such as.
The beneficial effects of the invention are as follows：
There is the copper particle of high dispersive, active constituent utilization rate is high, adds after modified by silver carbonization thunder damping copper alloy particle activation
Hydrogen activity is high, and operation air speed is high；Modified by silver is carbonized raney copper catalyst to realize high copper loading, and silver can isolate gold
Belong to copper activity component, effectively extend the service life of catalyst, and the doping of silver reduces the loss late of 1,3-butadiene.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Raw materials used in embodiment is commercially available.
Embodiment 1
(1) by liquid-state epoxy resin (Ba Ling petrochemical industry, CYD-128) 100 mass parts, curing agent methyl tetrahydro phthalic anhydride
(MeTHPA) (the Guangdong flourishing age reaches science and trade limited company) 85 mass parts, curing accelerator triethanolamine (TEA) (Tianjin
Learn reagent one factory) 1.5 mass parts stir evenly.
(2) epoxy systems prepared in 50g steps (1) are weighed and 150g copper-aluminium alloy powders are thoroughly mixed, copper aluminium closes
Cu contents are 50% (weight) in gold, and aluminium content 50% (weight), takes appropriate mixture to be added in cylindrical die, use tablet
Vulcameter is molded 30mins under conditions of 120 DEG C of temperature, pressure 7MPa, with compression molding instrument in 150 DEG C of temperature, pressure 7MPa
Under conditions of be molded 90mins, cooling is taken out, and obtains 2.0mm × 3.0mm or so cylindrical catalyst precursors；
(3) 100ml catalyst precarsors are measured, are put into tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, carburizing temperature
950 DEG C, when holding 2 is small, nitrogen is protected, nitrogen flow 200ml/min, and the copper aluminium conjunction that is carbonized is obtained after nitrogen protection cooling
Gold；
(4) with deionized water configuration 20%NaOH aqueous solutions (sodium hydroxide quality 100g), carbonization obtained by step (3) is added
Albronze 50mL, keep 85 DEG C of temperature, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washing
To washing lotion pH=8, deposit in spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 2.3mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 5：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL (about 15g) obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 5mL (silver-colored content is 15mg, accounts for the 0.1wt% of catalyst quality) in (1), reaction 2 it is small when after it is filtered molten
Liquid obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.28wt%.
Embodiment 2
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) with deionized water configuration 20%NaOH aqueous solutions (sodium hydroxide quality 100g), catalysis obtained by step (3) is added
Agent 50ml, keeps 85 DEG C of temperature, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washing washing lotion pH
=8, deposit in spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 2.3mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 5：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL (about 15g) obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 5mL in (1) (silver-colored content accounts for the 0.1wt% of catalyst quality for 15mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.24wt%.
Embodiment 3
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；150 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 6 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 2.3mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 5：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL (about 15g) obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 15mL in (1) (silver-colored content accounts for the 0.3wt% of catalyst quality for 45mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.73wt%.
Embodiment 4
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；600 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 2.3mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 5：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 13mL in (1) (silver-colored content accounts for the 0.26wt% of catalyst quality for 39mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.96wt%.
Embodiment 5
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 2.3mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 5：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 26mL (silver-colored content is 78mg, accounts for the 0.52wt% of catalyst quality) in (1), reaction 2 it is small when after it is filtered
Solution, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, measures the content of catalyst surface silver
For 1.86wt%.
Embodiment 6
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), add deionized water 10mL aqueous solutions and stir
Mix to dissolving, measure ethylenediamine solution 0.5mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 1：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 15mL in (1) (silver-colored content accounts for the 0.3wt% of catalyst quality for 45mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.69wt%.
Embodiment 7
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure ethylenediamine solution 4.6mL (ethylenediamine density 0.9g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of ethylenediamine and silver is 10：1, the solution of ethylenediamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 15mL in (1) (silver-colored content accounts for the 0.3wt% of catalyst quality for 45mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.56wt%.
Embodiment 8
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure triethanolamine solution 1.9mL (triethanolamine density 1.1g/mL) and be added dropwise in 10mL deionized waters, be made into
Homogeneous solution.The molar ratio of triethanolamine and silver is 2：1, the solution of triethanolamine is added dropwise in silver nitrate solution, shape
Into the solution of clear homogeneous, and by solution constant volume in 200mL volumetric flasks, the silver-colored source solution of 3.0mgAg/mL is formed.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 15mL in (1) (silver-colored content accounts for the 0.3wt% of catalyst quality for 45mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.68wt%.
Embodiment 9
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, measure isopropyl amine aqueous solution 1.9mL (isopropylamine density 0.7g/mL) and be added dropwise in 10mL deionized waters, be made into uniformly
Solution.The molar ratio of isopropylamine and silver is 4：1, the solution of isopropylamine is added dropwise in silver nitrate solution, is formed transparent equal
Even solution, and by solution constant volume in 200mL volumetric flasks, form the silver-colored source solution of 3.0mgAg/mL.
(6) measure the catalyst 30mL [about 15g] obtained by step (4) to be added in 50mL deionized waters, step is added dropwise
Suddenly silver-colored source solution 15mL in (1) (silver-colored content accounts for the 0.3wt% of catalyst quality for 45mg), when reaction 2 is small after it is filtered molten
Liquid, obtains silver-carbonization raney copper catalyst, detects silver content in catalyst using XRF, the content for measuring catalyst surface silver is
0.71wt%.
Embodiment 10
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh silver nitrate 1.2g (moles：7.1mmol), deionized water 10mL aqueous solutions are added to stir
Mix to dissolving, hydrochloric acid solution (palladium content 50mg/mL) 8mL of palladium bichloride is added dropwise, measure ethylenediamine solution 2.3mL (second two
Amine density：0.9g/mL, the mole of ethylenediamine：38mmol) it is added dropwise in 10mL deionized waters, is made into homogeneous solution.Ethylenediamine
Molar ratio with silver is 5：1, the molar ratio of ethylenediamine and Pd are 10：1, ethylenediamine solution is added dropwise to silver nitrate and chlorine
In the solution for changing palladium, form the solution of clear homogeneous, and by solution constant volume in 200mL volumetric flasks, formed 2.0mgPd/mL and
The silver-colored source solution of 3.0mgAg/mL.
(6) measure raney copper catalyst 30mL (about 15g) to be added in 50mL deionized waters, be added dropwise in step (5)
(silver-colored content is 45mg to silver-colored source solution 15mL, and the content of palladium is 30mg, and silver accounts for the 0.3wt% of catalyst quality, and palladium accounts for catalyst
The 0.2wt% of quality), reaction 2 it is small when after filtered solution, utilize XRF detection catalyst in silver content, be made silver-carbonization thunder
Buddhist nun's copper catalyst, the content for measuring catalyst surface silver are 0.73wt%, and the content of palladium is 0.12wt%.
Embodiment 11
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
Degree 85 DEG C, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to washing lotion pH=8, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh AgNO31.2g (moles：7.1mmol), Ni (NO3)2·6H2O11g (moles：
38mmol) add deionized water 50mL aqueous solutions to stir to dissolving, hydrochloric acid solution (the palladium content 50mg/ of palladium bichloride is added dropwise
ML) 20mL, measures ethylenediamine solution 2.3mL (ethylenediamine density：0.9g/mL, the mole of ethylenediamine：38mmol) it is added dropwise to
In 10mL deionized waters, homogeneous solution is made into.The molar ratio of ethylenediamine and silver is 5：1, the molar ratio of ethylenediamine and Ni are 1：1,
The molar ratio of ethylenediamine and Pd are 4：1, the solution of clear homogeneous is formed, by solution constant volume in 200mL volumetric flasks, is formed
The silver-colored source solution of 3.0mgAg/mL, 10mgNi/mL, 5.0mgPd/mL.
(6) measure raney copper catalyst 30mL (about 15g) to be added in 50mL deionized waters, be added dropwise in step (5)
(silver-colored content is 45mg to silver-colored source solution 15mL, and the content of nickel is 150mg, and the content of Pd is 75mg；Silver accounts for catalyst quality
0.3wt%, nickel account for the 1.0wt% of catalyst quality, and palladium accounts for the 0.5wt% of catalyst quality), reaction 2 it is small when after it is filtered molten
Liquid, detects silver content in catalyst using XRF, silver-raney copper catalyst is made, the content for measuring catalyst surface silver is
0.73wt%, the content of palladium is 0.28wt%, and the content of nickel is 0.89wt%.
Comparative example 1
After albronze is ground into the alloy block of 0.9-3.2mm or so, 20% sodium hydroxide is slowly added in batches
In solution, soak time 2h.Catalyst after above-mentioned steps are handled washs 1000mL washings with 20~40 DEG C of deionized water
20-40 times to washing lotion pH value be 7~9.
Comparative example 2
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
85 DEG C of degree, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to close to after neutral, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh 15.6g silver nitrates and be dissolved in constant volume in 100mL volumetric flasks, silver-colored content is 100mg/
mL。
(6) measure the catalyst 30mL (about 15g) obtained by step (4) to be added in 50mL deionized water solutions, add step
Suddenly silver nitrate solution 5mL in (5) (silver-colored content is 500mg, and silver accounts for the 3.3wt% of catalyst quality), when reaction 2 is small after filter
Cross solution, silver-colored content is 1.38wt% in final catalyst.
Comparative example 3
(1) powdered phenol-formaldehyde resin is sufficiently mixed with curing agent hexamethylenetetramine with homogenizer, six methines four
Amine is 12/100 with phenolic resin weight ratio；100 grams of mixtures and 300 grams of copper-aluminium alloy powders are fully mixed with homogenizer
Close, Cu contents are 50% (weight) in albronze, aluminium content 50% (weight)；
(2) tablet press machine is warming up to 90 DEG C, above material is put into mould and is molded on tablet press machine, is shaped to
The sheet material of 2mm thickness；Tablet press machine is warming up to 150 DEG C, the sheet material of forming is placed again into mould the 5MPa on tablet press machine
Cure 10min under pressure；The 2mm thick sheets being cured are cut into 3-5mm rectangle little particles；
(3) 100mL little particles are measured, are carbonized in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, 650 DEG C of furnace temperature, is protected
Hold 3 it is small when, nitrogen protection, flow 200mL/min；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
85 DEG C of degree, 1 it is small when after filter out solution, that is, the carbonization raney copper catalyst activated, washs to close to after neutral, deposits in
It is spare in deionized water.
(5) silver-colored solution is prepared：Weigh 15.6g silver nitrates and be dissolved in constant volume in 100mL volumetric flasks, silver-colored content is 100mg/
mL。
(6) measure the catalyst 30mL obtained by step (4) to be added in 50mL deionized water solutions, add in step (5)
Silver nitrate solution 8mL (silver-colored content is 800mg, accounts for the 5.3wt% of catalyst quality), reaction 2 it is small when after filtered solution, most
Silver-colored content is 0.89wt% in whole catalyst.
Comparative example 4
Weigh 102g Cu (NO3)2·3H2O,174g Al(NO3)3·9H2O is configured to the copper nitrate and nitre that concentration is 2.0M
The mixing salt solution of sour aluminium, adds in 15mL addition 1 steps of embodiment (3) with preparation after being uniformly mixed into mixed solution
Silver nitrate solution 9mL (wherein Ag contents are 100mg/mL)；50g NaOH are claimed constantly to be stirred in 200mL deionized waters
It is lower that sodium hydroxide solution is poured slowly into the mixed solution of three kinds of metal salts, pH value is adjusted as neutrality.After solution is filtered
It is washed with deionized and three times, is filtered after being dried overnight in 100 DEG C of drying baker again, tabletting after 5h is roasted at 400 DEG C
Shaping, the content that obtained Cu contents are about 40%, Ag are 2%.
Embodiment 12
Bed experiment is fixed in the above-mentioned catalyst of preparation, reaction condition is as follows：
Reactor is two sections of fixed bed reactors, and every section of dress catalyst 10mL, by Catalyst packing into reactor, uses
After nitrogen conversion, reactor is passed through after c4 fraction is matched somebody with somebody hydrogen.The composition (fraction) of c4 fraction is as shown in table 1.Reaction condition
For：Hydrogen Vapor Pressure 1.0Mpa, two reactor inlet temperature are 45 DEG C, and the molar ratio of hydrogen/alkynes is 2~4, and liquid hourly space velocity (LHSV) is
10-20h-1.The content of each component in c4 fraction is measured using gas chromatography.
Above-mentioned catalyst c4 fraction selection hydrogenation catalyst performance is evaluated, wherein embodiment 1-4 and comparative example 1-3
Directly evaluated, comparative example 4 evaluate before at 150 DEG C using hydrogen purge 2 it is small when be allowed to reduction evaluated again, at 45 DEG C
Under, always the loss of alkynes amount and butadiene is listed in table 2 after each hydrogenation of catalyst carbon four.
The raw material composition of 1 carbon four of table
| Component | Material content (wt%) | Component | Material content (wt%) |
| Iso-butane | 2.30 | 1,2- butadiene | - |
| Normal butane | 6.33 | 1,3- butadiene | 48.19 |
| Trans-2-butene | 4.14 | Allylene | 0.10 |
| 1- butylene | 12.69 | Ethyl acetylene | 0.76 |
| Isobutene | 22.97 | Vinylacetylene | 0.12 |
| Cis-2-butene | 2.31 |
2 carbon of table, four selective hydrogenation removes alkynes result of the test
It can be drawn by four acetylene hydrogenation result of the test of carbon：
By the use of organic amine as complexing agent prepare silver load raney copper catalyst can under high-speed (>10h-1) entering
Alkynes in mouth C-4-fraction is removed to below 30ppm, and the loss late of 1,3-butadiene can be controlled below 3.0%；
The doping of silver can be accurately controlled as prepared by silver-colored source by stablizing silver complex by the use of Amine Solutions, and be used
The raney copper catalyst for the modified by silver that silver nitrate is prepared as silver-colored source but fails the doping of accurately control silver.
The silver carbonization raney copper catalyst and unmodified raney copper catalyst 1,3- prepared by the use of silver nitrate as silver-colored source
The loss of butadiene it is higher (>3%).Compared with raney copper catalyst, although under slightly having in silver carbonization raney copper catalyst activity
Drop, the loss of the 1,3-butadiene but effectively reduced.And aluminium oxide as carrier Cu-series catalyst (comparative example 4) in high-speed
Lower acetylene removal ability is substantially insufficient.
Claims (10)
- A kind of 1. preparation method of silver carbonization raney copper catalyst, it is characterised in that the described method includes：(1) Raney alloy particle is uniformly mixed with the curing system for the organic matter that can be carbonized, then cured, before obtaining catalyst Body；The weight ratio of Raney alloy particle and the organic matter curing system that can be carbonized is 1：99~99：1；The curing system for the organic matter that can be carbonized includes the organic matter and additive that can be carbonized；The organic matter being carbonized is to have Machine high-molecular compound；(2) under inert gas shielding, high temperature cabonization catalyst precarsor obtained above, then activated to obtain carbonization Lei Nitong Catalyst；(3) soluble organic amine and water are made into mixed solution, are redissolved soluble silver salt and the soluble-salt of other auxiliary agents, system It is standby into silver-colored source solution；The molar ratio of organic amine and silver salt solution is 1：1~10:1；Other auxiliary agents include Co, Fe, Mn, Ni, Zn, the one or more in Cr, Pd；The molar ratio of organic amine and auxiliary agent is 1：2~10:1；The solubility organic amine is ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine, diethyl Amine, isopropylamine, aniline, N, one in accelerine, lauryl amine, triethylene diamine, cyclohexylamine and six tetramethyl urotropines Kind is several；(4) carbonization raney copper catalyst is added in deionized water and aaerosol solution is formed by stirring, by above-mentioned steps (3) In silver-colored source solution be added dropwise to carbonization raney copper catalyst solution in, reaction 1~2 it is small when, after washing be made silver carbonization thunder Buddhist nun's copper catalyst；Silver-colored quality is 0.01w%~1.0wt% of carbonization raney copper catalyst in silver-colored source solution；The quality of promoter metal is 0~5wt% of carbonization raney copper catalyst in silver-colored source solution.
- 2. the preparation method of silver carbonization raney copper catalyst as claimed in claim 1, it is characterised in that：The organic high molecular compound is epoxy resin, phenolic resin, furane resins, polystyrene, styrene-divinylbenzene At least one of copolymer, polyacrylonitrile, starch, viscose rayon, lignin, cellulose, butadiene-styrene rubber, polyurethane rubber；The additive is curing accelerator, dyestuff, pigment, colouring agent, antioxidant, stabilizer, plasticizer, lubricant, stream Dynamic modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modifying agent, One kind or combination in demolding aids, nucleator；The solubility organic amine is triethanolamine, monoethanolamine, the one or more of ethylenediamine and hexamethylene diamine.
- 3. the preparation method of silver carbonization raney copper catalyst as claimed in claim 2, it is characterised in that：The weight ratio of the Raney alloy particle and the organic matter curing system that can be carbonized is 10：90~90：10；The molar ratio of organic amine and silver salt solution is 2:1~5:1；Silver-colored quality is 0.1wt%~0.6wt% of carbonization raney copper catalyst in silver-colored source solution；The quality of promoter metal is 0.2wt%~1wt% of carbonization raney copper catalyst in silver-colored source solution.
- 4. the preparation method of silver carbonization raney copper catalyst as claimed in claim 3, it is characterised in that：The weight ratio of the Raney alloy particle and the organic matter curing system that can be carbonized is 25：75~75.
- 5. the preparation method of silver carbonization raney copper catalyst as claimed in claim 1, it is characterised in that：Carburizing temperature is 400~1200 DEG C in step (2)；Protective gas is the inert gas such as nitrogen or argon gas, carbonization 1~12 Hour.
- 6. the preparation method of silver carbonization raney copper catalyst as claimed in claim 5, it is characterised in that：Carburizing temperature is 600~950 DEG C in step (2).
- 7. the preparation method of silver carbonization raney copper catalyst as claimed in claim 6, it is characterised in that：In step (3), silver-colored soluble-salt is nitrate, and other promoter soluble salts are nitrate, chloride or acetate.
- 8. the preparation method of silver carbonization raney copper catalyst as claimed in claim 1, it is characterised in that：Raney alloy includes metallic copper and metallic aluminium.
- A kind of 9. silver carbonization raney copper catalyst prepared by method as described in one of claim 1~8.
- 10. silver carbonization raney copper catalyst prepared by a kind of method as described in one of claim 1~8 is in four acetylene hydrogenation of carbon In application, it is characterised in that：Reaction inlet temperature be 30 DEG C~60 DEG C, reaction pressure is 0.5~2.0MPa, the liquid volume metering with c4 fraction Reaction velocity be 2~20h-1, under conditions of hydrogen and alkynes volume ratio be 0.2~10mol/mol, by alkynes in liquid phase c4 fraction Hydrocarbon is removed to below 30ppm, and 1,3-butadiene loss late is controlled below 3%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111085222A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc carbon raney copper catalyst and preparation method and application thereof |
| CN111085223A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-loaded-zinc-doped Raney copper catalyst and preparation method and application thereof |
| CN111085221A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc doped Raney copper catalyst and preparation method and application thereof |
| CN112791734A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Silver and nitrogen doped Raney copper zinc carbide catalyst and preparation method and application thereof |
| CN112791733A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Preparation method of silver-carbonized raney copper catalyst, catalyst and application |
| CN114452993A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of Raney copper carbide catalyst, catalyst and method for preparing ethanol by acetate hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111085222A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc carbon raney copper catalyst and preparation method and application thereof |
| CN111085223A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-loaded-zinc-doped Raney copper catalyst and preparation method and application thereof |
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| CN112791734A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Silver and nitrogen doped Raney copper zinc carbide catalyst and preparation method and application thereof |
| CN112791733A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Preparation method of silver-carbonized raney copper catalyst, catalyst and application |
| CN112791734B (en) * | 2019-10-28 | 2022-09-20 | 中国石油化工股份有限公司 | Silver and nitrogen doped Raney copper zinc carbide catalyst and preparation method and application thereof |
| CN114452993A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of Raney copper carbide catalyst, catalyst and method for preparing ethanol by acetate hydrogenation |
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