CN109701557A - Composite catalyst, composite catalyst of activation and its preparation method and application - Google Patents
Composite catalyst, composite catalyst of activation and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to catalyst field, it is related to a kind of composite catalyst, composite catalyst of activation and its preparation method and application.The composite catalyst includes: continuous phase carbon, dispersed phase Raney alloy particle and dispersed phase titanium-containing oxide, wherein dispersed phase Raney alloy particle and dispersed phase titanium-containing oxide are respectively evenly or uniformly dispersed in continuous phase carbon, the continuous phase carbon is by obtaining after at least one organic carbon being carbonized, and the titanium-containing oxide is thermally decomposed to yield through titaniferous sol-gel.Catalyst of the invention is a kind of using carbon, titanium-containing oxide, active metal as the composite catalyst of matrix, titanium-containing oxide both can in the case where carbon flow is lost carrier as reinforcing particle intensity, catalyst surface acidity, adjustable catalysis reaction selectivity are provided simultaneously.
Description
Technical field
The invention belongs to industrial catalyst fields, and in particular, to a kind of composite catalyst, a kind of activation it is compound
Catalyst and their preparation method and application.
Background technique
In catalytic field, " Lei Nifa " is a kind of preparation method of active metal catalyst, this method comprises: i) first making
The alloy and ii of the standby above component of the binary containing active metal) then at least one metal component is extracted, it is left tool
There is the metal component of porous structure and higher catalytic activity.Step ii) also referred to as " activate ".For example, U.S. M.Raney is earliest
Raney's nickel catalyst (Industrial and Engineering Chemistry, 1940, Vol.32,1199) has been invented, it should
Catalyst is prepared via a method which: first being prepared nickel alumin(i)um alloy, is then dissolved the aluminium element in alloy with strong base solution, is left tool
There are porous structure, the nickel metal with very high catalytic activity.
Reni catalyst has Raney's nickel catalyst, thunder Buddhist nun Co catalysts, raney copper catalyst etc., wherein with raney ni catalysis
Agent is most commonly seen, and Raney's nickel catalyst usually occurs with powdery form, inflammable, inconvenient, is chiefly used in fine chemistry industry neck
In the middle and small scale catalytic hydrogenation reaction of domain, and it is not used to general fixed bed reaction.
In order to extend the application field of Raney's nickel catalyst, takes certain method to be formed, especially processed
It is research direction more concerned in recent years at fixed bed catalyst.
Patent application CN1557918A discloses a kind of molding Raney's nickel catalyst and preparation method thereof, the catalyst be by
One of aluminium and Ni, Co, Cu, Fe or a variety of component alloy powder are adopted using inorganic matters such as boehmites as adhesive
The organic substance for using sesbania powder, carboxymethyl cellulose etc. natural or synthetic is directly mediated, molding, roasting as duct template,
And activate and be made through caustic solution, gained catalyst has certain shape and intensity, may be used as fixed bed catalyst.But
The catalyst preparation process is complicated, needs to roast under 900 DEG C of high temperature, and high-temperature roasting causes considerable particle to be sintered, so that
The utilization rate of active metal is lower, thus catalyst activity is lower.And obtained catalyst contains inorganic oxide carrier
(such as aluminium oxide, silica), the acid-base property of carrier causes the selectivity of catalyst lower.In addition, the catalyst recycles metal
It is difficult, seriously polluted.
It is starting material that patent US5536694, which discloses one kind by alloy powders such as Ni, Al, Co, using lubricant, plasticizing
The adjuvant powders such as agent are formed, be fired, lye activation and etc. obtain preformed catalyst.The catalyst preparation process is multiple
It is miscellaneous, need to roast under 700-850 DEG C of high temperature, high-temperature roasting causes considerable particle to be sintered so that the utilization rate of metal compared with
Low, amorphous state Raney metal is reduced, and leads to active reduction.
In short, preparing fixed bed raney catalyst by powder metallurgy, forming operation is difficult, and preparation cost is higher, is forming
It needs that various auxiliary agents are added in the process, residual impurity content is very high after molding, and catalyst activity and selectivity will receive forming process
The influence of middle residual auxiliary agent, and high-temperature roasting will cause considerable particle sintering, and amorphous state Raney metal is reduced, to lead
Activation reduces.
Sinopec house journal application CN201410083872 discloses a kind of composite catalyst, main component packet
Include: continuous phase carbon, dispersed phase Raney alloy particle wherein dispersed phase Raney alloy uniform particle or are non-uniformly dispersed in continuous
In phase carbon, the continuous phase carbon is obtained after being carbonized by or mixtures thereof the organic matter that can be carbonized.The catalyst preparation side
Method is simple, and cost is relatively low, and obtained catalyst is highly active, and catalyst granules intensity is good.The patent application obtains
A kind of practical fixed bed raney catalyst for having industrial application value, but it also has shortcoming, and one side carbon is as bone
Frame high temperature antioxygen property is not strong, is easy to happen oxidation wastage under oxygen atmosphere or oxygenatedchemicals hot conditions, granule strength by
Damage, then causes catalyst granules dusting, reactor plugs influence to keep the safety in production；On the other hand, carbon skeleton surface nature is close
Neutrality, it is not applicable to certain reactions for needing acid auxiliary.
Therefore, develop a kind of high temperature oxytolerant, the fixed bed raney catalyst with surface acidity there is very high reality
Application value.
Summary of the invention
The object of the present invention is to provide a kind of thunder Buddhist nun's composite catalyst that can be used for fixed bed, the catalyst preparation mistakes
Journey is simple, and catalyst granules intensity can be kept in oxygen atmosphere, has both porous carbon and titanium-containing oxide surface nature.
The first aspect of the present invention provides a kind of composite catalyst comprising: continuous phase carbon, dispersed phase Raney alloy grain
Son and dispersed phase titanium-containing oxide, wherein dispersed phase Raney alloy particle and dispersed phase titanium-containing oxide be respectively uniformly or non-uniformly
Ground is dispersed in continuous phase carbon, the continuous phase carbon be by being obtained after at least one organic carbon being carbonized, it is described to contain
Titanium oxide is thermally decomposed to yield through titaniferous sol-gel.
A preferred embodiment of the invention, the Raney alloy particle include Raney metal and can be leached
Element.Term " Raney metal " used herein refers to metal insoluble, with catalytic activity when being activated with Lei Nifa.Institute
It states Raney metal and is preferably selected from least one of nickel, cobalt, copper and iron.Term " element that can be leached " used herein is
Refer to the element that can be dissolved when being activated with Lei Nifa.The element being leached is preferably selected from least one in aluminium, zinc and silicon
Kind.
In a preferred embodiment, the Raney alloy is selected from nickel alumin(i)um alloy, cobalt aluminium alloy, albronze.
In one embodiment, the weight ratio of the Raney metal and the element being leached is 1:99-10:1,
Preferably 1:10-4:1.
In order to improve catalyst activity or selectivity, Raney alloy may be incorporated into promotor, form multicomponent mixture
Raney alloy, the promotor are selected from least one of Mo, Cr, Ti, Pt, Pd, Rh and Ru.The content of the promotor is preferably
The 0.01-5wt% of Raney alloy particle total weight.
Term " organic matter that can be carbonized " used herein refers to those organic matters, can be by certain temperature
With processing under the conditions of oxygen deprivation or oxygen-free atmosphere so that the whole or big portion of the non-carbon elements such as hydrogen therein, oxygen, nitrogen, sulphur vapors away and turns
Change the higher synthetic material of phosphorus content into.Obtained carbon containing synthetic material has high temperature resistant, high intensity, high-modulus, porous etc.
Performance.
In one embodiment, the organic matter being carbonized is preferably organic high molecular compound, including is naturally had
Machine high-molecular compound and synthetic organic polymer compound.
In a preferred embodiment, the organic matter being carbonized is selected from rubber, thermosetting plastics and thermoplasticity
The synthetic organic polymer compound of at least one of plastics；The rubber is preferably butadiene-styrene rubber and/or polyurethane rubber；Institute
It states thermosetting plastics and is preferably selected from least one of epoxy resin, phenolic resin and furane resins；The thermoplastic is excellent
Choosing is selected from least one of polystyrene, styrene-divinylbenzene copolymer and polyacrylonitrile.
In another preferred embodiment, the organic matter being carbonized be selected from starch, modified starch, viscose rayon,
The natural organic polymer compounds of at least one of lignin, cellulose and carboxymethyl cellulose.
In yet another preferred form, the organic matter being carbonized is selected from coal, bitumen, asphalt and coal tar
At least one of pitch.
The organic matter being carbonized can also be high for the conduction selected from least one of polyaniline, polypyrrole and polythiophene
Molecular compound.
In the present invention, the titanium-containing oxide is preferably titanyl compound, is specifically preferably selected from TiO, TiO2And Ti2O3In
At least one.The titanium-containing oxide is thermally decomposed to yield via titaniferous sol-gel.Wherein, titaniferous colloidal sol can be used
The various conventional methods in this field obtain, it is preferable that the titaniferous colloidal sol is obtained by metatitanic acid ester hydrolysis, and the hydrolysis is usually in second
It is carried out in alcohol medium；The titanate esters are preferably tetraisopropyl titanate and/or butyl titanate.
The content of Raney alloy particle can change in a wide range in composite catalyst of the invention, titaniferous oxidation
The content of object can also determine as needed, it is preferable that with the total weight of composite catalyst, the content of Raney alloy particle is
10-90wt%.
In the present invention, due to the difference of composite catalyst expected property and purposes, the content of titanium-containing oxide can be very wide
In the range of change, in terms of titanium elements, the content of the titanium-containing oxide can be 0.5wt%-50wt%.According to the present invention one
Kind specific embodiment, the content of the titanium-containing oxide can be 1wt%-20wt%.
The granular size of Raney alloy particle of the present invention can select in a wide range.For example, average grain diameter can be
0.1-1000 microns, preferably 1-500 microns, more preferably 10-100 microns.
The present invention does not have special limitation to the shape of the composite catalyst, as long as it is suitble to fixed bed or fluidized bed
Technique.Expediently, the composite catalyst can be in sphere, hemisphere, ring bodies, half-annuli, cylindrical body, semicolumn
The combination of body, hollow cylinder, prism, cuboid, cube, tooth form object, irregular particle shape or the above shape.
The granular size of composite catalyst of the invention can change in a wide range, depend on preparation method and catalyst
Desired use.The average equivalent diameter of the composite catalyst preferably exists typically within the scope of 0.3mm-20mm
Within the scope of 0.5mm-10mm, more preferably within the scope of 1mm-8mm.
Carbon, titanium-containing oxide, Raney alloy are combined together by the present invention by the molding method of Process Technology of Polymer,
It is prepared for the Raney metal composite catalyst suitable for fixed bed.On the one hand the organic matter that can be carbonized is mixed with Raney alloy
After be carbonized, obtain the compound of carbon and Raney alloy, Raney alloy plays facilitation to carbonisation, can make to be carbonized
Carry out more complete, after carbonization, Raney alloy is dispersed in the continuous phase of carbon, and is firmly combined with continuous phase carbon, continuous phase
Carbon itself have porous structure so that composite catalyst have it is very high-intensitive, simultaneously as Raney alloy particle distribution is porous
In carbon continuous phase, solution can easily touch Raney alloy particle, and in activation process, Raney alloy particle is easy to
It is activated to form porous high activity Raney metal, and since a small amount of agraphitic carbon is also washed away in activation process,
To enable the reaming of continuous phase carbon material and more Raney alloys is enable to expose.Therefore, the catalysis after present invention activation
Agent has very high catalytic activity.On the other hand, titanium-containing oxide plays auxiliary skeleton function and provides different from carbon surface property
Effect, such as promote the surface acidity of chemical reaction, therefore, catalyst of the invention also has better intensity, and special
It is not applicable to the reaction of acid auxiliary.
The second aspect of the present invention provides a kind of method for preparing above-mentioned composite catalyst comprising following steps:
A, curable compositions are prepared, the curable compositions or its cured product include the organic matter that can be carbonized；It is described
Solidification composition filling can be liquid, gluey, paste or powdered；
B, Raney alloy particle, titaniferous colloidal sol are mixed with the obtained curable compositions of step a, is then made obtained
Mixture solidification, and optionally crush cured mixture, obtain catalyst precarsor；
C, composite catalyst is made under inert gas protection, catalyst precarsor described in high temperature cabonization.
In the method for the invention, the Raney alloy particle, titaniferous colloidal sol and the organic matter that can be carbonized such as first aspect
It is described.
A kind of specific embodiment according to the present invention, prepare the method for the composite catalyst the following steps are included:
A, curable compositions are often prepared with curing formula according to the organic matter that can be carbonized, the curable compositions are liquid
Body shape is powdered；Titanate esters are hydrolyzed, titaniferous colloidal sol is obtained；
B, Raney alloy particle, titaniferous colloidal sol are uniformly mixed with the curable compositions that step a is obtained, then makes gained
The mixture molded curing arrived, titaniferous colloidal sol become gel, obtain catalyst precarsor；
C, composite catalyst is made under inert gas protection, catalyst precarsor described in high temperature cabonization.
The composition of the curable compositions generally depends on the selected organic matter being carbonized.In some embodiments
In, when the selected organic matter being carbonized is thermoplastic, the curable compositions can be substantially by the warm
The powder of thermoplastic plastic forms.Such curable compositions can be solidified by heating-cooling.
In other embodiments, the curable compositions may include the organic matter that can be carbonized and solvent and/
Or liquid dispersant.Such curable compositions can by least partly remove the solvent and/or liquid dispersant come
Solidification.The example of the solvent and liquid dispersant includes but is not limited to water；C1-C8Alcohol, such as methanol, ethyl alcohol, isopropanol, just
Butanol, 2-Ethylhexyl Alcohol；Ester, such as ethyl acetate, methyl acetate；Ketone such as acetone, methyl ethyl ketone, cyclohexanone；C5-C30Hydrocarbon, such as penta
Alkane, pentamethylene, hexane, hexamethylene, heptane, octane, decane, dodecane, benzene,toluene,xylene；C1-C10Halogenated hydrocarbons.In this way
Curable compositions in the lower limit of the concentration of organic matter that can be carbonized can be 5,10,15,20,25,30,35 or 40wt%,
And the upper limit can be 20,30,40,45,50,55,60,65,70,75,80,85,90 or 95wt%.
In other embodiments, the curable compositions may include thermosetting resin and solidification if necessary
Agent.Such curable compositions can be solidified by heating.Curing system suitable for different thermosetting resins is ability
Known to field technique personnel.
One or more additives selected from the following can be optionally added when preparing the curable compositions: bonding
Agent, curing accelerator, dyestuff, pigment, colorant, antioxidant, stabilizer, plasticizer, lubricant, flow ability modifying agent help
Agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modifying agent, demolding aids, nucleation
Agent etc..Additive therefor dosage is conventional amount used, or can requirement according to the actual situation be adjusted.
The curable compositions of preparation can be liquid system, liquid-solid system, gluey system or powdery solid system.Liquid
Body system can be evenly mixed；Pulverized solid system can directly be blended uniformly；Granulated solid system is available industrial common
Any disintegrating apparatus crush after be blended it is uniform.
In stepb, the weight for the curable compositions that Raney alloy particle, the total weight of titaniferous colloidal sol and step a are obtained
Measuring ratio can be 10:90-90:10, preferably 25:75-75:25.
In step b, by the way that the mixture of Raney alloy particle, titaniferous colloidal sol and curable compositions is solidified and optionally will
Cured mixture crushes, and obtains catalyst precarsor.Curing mode and process conditions depend on the group of the curable compositions
At, and can be readily determined by those skilled in the art.For example, if thermoplastic resin is used as in curable compositions
Can carbonization organic matter, then can be by the way that the mixture of the Raney alloy particle and curable compositions be heated to the heat
The solidification of curable compositions more than the softening temperature of plastic resin is realized with then cooling；If thermosetting resin is used as
In curable compositions can carbonization organic matter, then can be by by the mixing of the Raney alloy particle and curable compositions
The solidification that object is heated to cause curing reaction to realize curable compositions；If natural organic polymer compounds such as starch,
Modified starch, cellulose, carboxymethyl cellulose and lignin be used as in curable compositions can carbonization organic matter, then can be with
Liquid medium in mixture and/or heating by removing the Raney alloy particle and curable compositions can be consolidated to realize
Change the solidification of composition.If desired, the cured mixture obtained by curing operation can use it is any known in the art
High-molecular organic material process equipment, by such as cutting, cutting, punching press or the methods of broken be processed into required shape
The particle of shape and size.
Carbonization, that is, high-temperature roasting described in step c, carries out, carburizing temperature is generally 400- generally in tubular heater
1200 DEG C, preferably 600-950 DEG C, protective gas are the inert gases such as nitrogen or argon gas, are carbonized 1-24 hours.For example, phenolic aldehyde
Resin 850 DEG C be carbonized 3 hours, can carbonization, form porous carbon.Higher carburizing temperature obtains after can making carbonization
Carbon it is more regular.Under Carbonization Conditions, the solidification of titaniferous colloidal sol, which is decomposed, obtains titanium-containing oxide.
Composite catalyst of the invention can be easy to be activated, and it is above-mentioned that the third aspect of the present invention provides a kind of activation
The method of composite catalyst, this method include the composite catalyst described in base extraction.
Specific base extraction activates the method for the composite catalyst and its condition used is substantially known.Example
Such as, the step of base extraction includes: and is activated with the lye of 0.5-30 weight % concentration described compound at 25 DEG C -95 DEG C
It type catalyst -72 hours 5 minutes, is activated with element that at least part dissolved out in Raney alloy can be leached.One
In kind preferred embodiment, the lye is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
The fourth aspect of the present invention provides a kind of composite catalyst of activation, and the composite catalyst of the activation is by above-mentioned
Method be made.
The present invention passes through the additional amount of Raney alloy in control catalyst preparation process and/or the activation journey of control catalyst
Degree, so as to easily control the load capacity of Raney metal in catalyst, such as available Raney metal load capacity is
Catalyst after the activation of 1-90 weight % (being in terms of 100% by overall catalyst weight), preferably Raney metal load capacity are 10-90 weight
Catalyst after measuring the activation of %, further preferred Raney metal load capacity are the catalyst after the activation of 30-80 weight %.This
After invention can also easily control activation by the additional amount of titaniferous colloidal sol in control composite catalyst preparation process
The content of titanium-containing oxide in catalyst.
Catalyst of the present invention is compound fixed-bed thunder Buddhist nun type catalyst, and surface nature has both the spy of carbon and titanium-containing oxide
Point, carbon skeleton can provide the catalyst surface and cellular structure close to neutrality, and titanium-containing oxide can provide surface acidity, increase
Granule strength of the powerful catalyst particle in oxygen atmosphere, even if part carbon skeleton is oxidized loss, but due to titanium-containing oxide
In the presence of, catalyst granules will not complete dusting, be conducive to reactor safe and stable operation.
Catalyst prepared by the present invention is especially suitable for adding hydrogen or dehydrogenation reaction.Since the catalyst is shaped catalyst
Agent, granule strength is good, can be used for fixed bed or moving bed.
The preparation method of catalyst of the present invention is simple, and cost is relatively low.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The present invention is described further for following example, but not thereby limiting the invention.
Embodiment 1
(1) butyl titanate and dehydrated alcohol are mixed according to mass ratio 1:1, above-mentioned mixed solution is taken to be added to deionization
In water, the molar ratio of mixed solution and water is 1:3, is stirred 2 hours at room temperature, and titaniferous colloidal sol is made.
(2) by 100 mass parts of titaniferous colloidal sol obtained in step (1), 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 liability company) 85 mass parts, solidification
1.5 mass parts of promotor triethanolamine (TEA) (Tianjin Chemical Reagents Factory No.1) stir, and obtain curable mixing
Objects system.
(3) it weighs the mixture system prepared in 60g step (2) and 180g Nickel Aluminium Alloy Powder is thoroughly mixed, nickel aluminium
Ni content is 48% (weight) in alloy, and aluminium content 52% (weight) takes appropriate mixture to be added in cylindrical die, with flat
Plate 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
90mins is molded under conditions of 7MPa, it is cooling to take out, obtain particulate catalyst precursor.
(4) 100ml catalyst precarsor is measured, is put into tubular type high-temperature electric resistance furnace, under the nitrogen flow of 200ml/min, with
10 DEG C/min of heating rate is warming up to 600 DEG C of carburizing temperature, is kept for 3 hours at such a temperature, then cools down, obtain compound urge
Agent.
(5) 20%NaOH aqueous solution 400g is configured with deionized water, and added it to compound obtained by 50ml step (4)
In catalyst.Obtained mixture is kept for 8 hours at 85 DEG C, then filters out solution, and by solids deionized water
Washing is to close neutrality, the composite catalyst activated.The composite catalyst of the activation is deposited in deionized water
It is spare.Nickel content of metal is about 50% (weight) in the composite catalyst of the activation, and the content of titanium elements is about 9%
(weight), the poidometer of the catalyst based on activation.
Embodiment 2
(1) butyl titanate and dehydrated alcohol are mixed according to mass ratio 1:1, above-mentioned mixed solution is taken to be added to deionization
In water, the molar ratio of mixed solution and water is 1:3, is stirred 2 hours at room temperature, and titaniferous colloidal sol is made.
(2) by 50 mass parts of titaniferous colloidal sol obtained in step (1), 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 liability company) 85 mass parts, solidification
1.5 mass parts of promotor triethanolamine (TEA) (Tianjin Chemical Reagents Factory No.1) stir, and obtain curable mixing
Objects system.
(3) it weighs the mixture system prepared in 55g step (2) and 180g Nickel Aluminium Alloy Powder is thoroughly mixed, nickel aluminium
Ni content is 48% (weight) in alloy, and aluminium content 52% (weight) takes appropriate mixture to be added in cylindrical die, with flat
Plate 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
90mins is molded under conditions of 7MPa, it is cooling to take out, obtain particulate catalyst precursor.
(4) 100ml catalyst precarsor is measured, is put into tubular type high-temperature electric resistance furnace, under the nitrogen flow of 200ml/min, with
10 DEG C/min of heating rate is warming up to 600 DEG C of carburizing temperature, is kept for 3 hours at such a temperature, then cools down, obtain compound urge
Agent.
(5) 20%NaOH aqueous solution 400g is configured with deionized water, and added it to compound obtained by 50ml step (4)
In catalyst.Obtained mixture is kept for 8 hours at 85 DEG C, then filters out solution, and by solids deionized water
Washing is to close neutrality, the composite catalyst activated.The composite catalyst of the activation is deposited in deionized water
It is spare.Nickel content of metal is about 50% (weight) in the composite catalyst of the activation, and the content of titanium elements is about 5%
(weight), the poidometer of the catalyst based on activation.
Embodiment 3
(1) butyl titanate and dehydrated alcohol are mixed according to mass ratio 1:1, above-mentioned mixed solution is taken to be added to deionization
In water, the molar ratio of mixed solution and water is 1:3, is stirred 2 hours at room temperature, and titaniferous colloidal sol is made.
(2) by 50 mass parts of titaniferous colloidal sol obtained in step (1), 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 liability company) 85 mass parts, solidification
1.5 mass parts of promotor triethanolamine (TEA) (Tianjin Chemical Reagents Factory No.1) stir evenly, and obtain curable mixing object
System.
(3) it weighs the mixture system prepared in 60g step (2) and 150g Nickel Aluminium Alloy Powder is thoroughly mixed, nickel aluminium
Ni content is 48% (weight) in alloy, and aluminium content 52% (weight) takes appropriate mixture to be added in cylindrical die, with flat
Plate 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
90mins is molded under conditions of 7MPa, it is cooling to take out, obtain particulate catalyst precursor.
(4) 100ml catalyst precarsor is measured, is put into tubular type high-temperature electric resistance furnace, under the nitrogen flow of 200ml/min, with
10 DEG C/min of heating rate is warming up to 600 DEG C of carburizing temperature, is kept for 3 hours at such a temperature, then cools down, obtain compound urge
Agent.
(5) 20%NaOH aqueous solution 400g is configured with deionized water, and added it to compound obtained by 50ml step (4)
In catalyst.Obtained mixture is kept for 8 hours at 85 DEG C, then filters out solution, and by solids deionized water
Washing is to close neutrality, the composite catalyst activated.The composite catalyst of the activation is deposited in deionized water
It is spare.Nickel content of metal is about 40% (weight) in the composite catalyst of the activation, and the content of titanium elements is about 6%
(weight), the poidometer of the catalyst based on activation.
Comparative example 1
This comparative example is used to illustrate the catalyst preparation of not titanium-containing oxide.
(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 liability company) 85 the mass parts, (Tianjin curing accelerator triethanolamine (TEA)
Learn one factory of reagent) 1.5 mass parts stir evenly.
(2) epoxy systems prepared in 50g step (1) are weighed and 150g Nickel Aluminium Alloy Powder is thoroughly mixed, nickel aluminium closes
Ni content is 48% (weight) in gold, and aluminium content 52% (weight) takes appropriate mixture to be added in cylindrical die, uses plate
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, it is cooling to take out, obtain particulate catalyst precursor.
(3) 100ml catalyst precarsor is measured, is put into tubular type high-temperature electric resistance furnace, under the nitrogen flow of 200ml/min, with
10 DEG C/min of heating rate is warming up to 700 DEG C of carburizing temperature, is kept for 3 hours at such a temperature, then cools down, obtain compound urge
Agent.
(4) 20%NaOH aqueous solution 400g is configured with deionized water, and added it to compound obtained by 50ml step (3)
In catalyst.Gained mixture is kept for 4 hours at 85 DEG C, then filters out solution, and solids is washed with deionized
To close neutrality, the composite catalyst activated.The composite catalyst of the activation is deposited in spare in deionized water.
Nickel content of metal is about 50% (weight), the poidometer of the catalyst based on activation in the composite catalyst of the activation.
Embodiment 4
It is strong and weak to compare catalyst surface acid-base property using probe reaction.
Compare the acid-base property on different catalysts surface with acetone hydrogenation reaction result: acetone hydrogenation reaction uses 200ml high
Reaction kettle test is pressed, reaction pressure 2.0MPa, reacts by 155 DEG C of reaction temperature, reactant dosage 100ml, catalyst amount 10ml
Time 8 hours.Embodiment and comparative example reaction result is as shown in table 1.
Methyl isobutyl carbinol is to be generated by acid catalysis effect, therefore its comparision contents catalyst can be used in hydrogenated products
Surface acidity relative size, methyl isobutyl carbinol content is higher, and it is acid strong to represent catalyst surface.
As it can be seen from table 1 the catalyst of embodiment 1-3, compared with the catalyst of comparative example 1, acid catalysis product methyl is different
Butyl carbinol content significantly improves, and illustrates that catalyst surface of the invention has comparable acidity, and determination is by containing titanyl
What compound component generated.
Methyl isobutyl carbinol content in acetone hydrogenation product in 1 different catalysts of table
To sum up, catalyst of the invention is a kind of to urge using carbon, titanium-containing oxide, active metal as the compound of matrix
Agent, titanium-containing oxide both can in the case where carbon flow is lost carrier as reinforcing particle intensity, while providing catalyst table
Face is acid, adjustable catalysis reaction selectivity.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (17)
1. a kind of composite catalyst comprising: continuous phase carbon, dispersed phase Raney alloy particle and dispersed phase titanium-containing oxide,
Wherein dispersed phase Raney alloy particle and dispersed phase titanium-containing oxide are respectively evenly or uniformly dispersed in continuous phase carbon, institute
Stating continuous phase carbon is by obtaining after at least one organic carbon being carbonized, and the titanium-containing oxide is through titaniferous colloidal sol-
What gel thermally decomposed to yield.
2. composite catalyst according to claim 1, wherein the Raney alloy particle includes Raney metal and can quilt
The element of leaching；The Raney metal is preferably selected from least one of nickel, cobalt, copper and iron；The element being leached is excellent
Choosing is selected from least one of aluminium, zinc and silicon；The weight ratio of the Raney metal and the element being leached is preferably 1:
99-10:1, further preferably 1:10-4:1.
3. composite catalyst according to claim 2, wherein the Raney alloy particle further include selected from Mo, Cr,
The promotor of at least one of Ti, Pt, Pd, Rh and Ru, the content of the promotor are the 0.01- of Raney alloy particle total weight
5wt%.
4. composite catalyst according to claim 1, wherein the organic matter being carbonized is selected from rubber, thermosetting
The synthetic organic polymer compound of at least one of property plastics and thermoplastic；
The rubber is preferably butadiene-styrene rubber and/or polyurethane rubber；
The thermosetting plastics is preferably selected from least one of epoxy resin, phenolic resin and furane resins；
The thermoplastic is preferably selected from least one in polystyrene, styrene-divinylbenzene copolymer and polyacrylonitrile
Kind.
5. composite catalyst according to claim 1, wherein the organic matter being carbonized is selected from starch, modification
The natural organic polymer compounds of at least one of starch, viscose rayon, lignin, cellulose and carboxymethyl cellulose.
6. composite catalyst according to claim 1, wherein the organic matter being carbonized be selected from coal, bitumen,
At least one of asphalt and coal tar pitch.
7. composite catalyst according to claim 1, wherein the organic matter being carbonized is selected from polyaniline, gathers
The conducting polymer compound of at least one of pyrroles and polythiophene.
8. composite catalyst according to claim 1, wherein the titanium-containing oxide is titanyl compound, is preferably selected
From TiO, TiO2And Ti2O3At least one of.
9. composite catalyst according to claim 1, wherein the titaniferous colloidal sol is obtained by metatitanic acid ester hydrolysis；It is described
Titanate esters are preferably tetraisopropyl titanate and/or butyl titanate.
10. composite catalyst described in any one of -9 according to claim 1, wherein the composite catalyst has
At least one of following characteristics:
With the total weight of composite catalyst, the content of Raney alloy particle is 10-90wt%；
The average grain diameter of the Raney alloy particle is 0.1-1000 microns；
The composite catalyst is in sphere, hemisphere, ring bodies, half-annuli, cylindrical body, semicylinder, hollow cylinder
The combination of body, prism, cuboid, cube, tooth form object, irregular particle shape or the above shape；
The composite catalyst is in granular form, and has the average equivalent diameter within the scope of 0.3mm-20mm.
11. a kind of method for preparing composite catalyst described in any one of claim 1-10 comprising following steps:
A, curable compositions are prepared, the curable compositions or its cured product include the organic matter that can be carbonized；
B, Raney alloy particle, titaniferous colloidal sol are mixed with the obtained curable compositions of step a, then makes obtained mixing
Object solidification, and optionally crush cured mixture, obtain catalyst precarsor；
C, composite catalyst is made under inert gas protection, catalyst precarsor described in high temperature cabonization.
12. according to the method for claim 11, wherein method includes the following steps:
A, curable compositions are often prepared with curing formula according to the organic matter that can be carbonized, the curable compositions are liquid
Or it is powdered；Titanate esters are hydrolyzed, titaniferous colloidal sol is obtained；
B, Raney alloy particle, titaniferous colloidal sol are uniformly mixed with the curable compositions that step a is obtained, is then made obtained
Mixture molded curing, titaniferous colloidal sol become gel, obtain catalyst precarsor；
C, composite catalyst is made under inert gas protection, catalyst precarsor described in high temperature cabonization.
13. method according to claim 11 or 12, wherein this method has at least one of following characteristics:
In stepb, the weight ratio for the curable compositions that Raney alloy particle, the total weight of titaniferous colloidal sol and step a are obtained
For 10:90-90:10, more preferably 25:75-75:25；
In step c, carburizing temperature is 400-1200 DEG C, and carbonization time is 1-24 hours；
In step c, inert gas is nitrogen or argon gas.
14. the method for composite catalyst described in a kind of any one of activation claim 1-10, this method includes using alkali
The liquid processing composite catalyst.
15. according to the method for claim 14, wherein the step of base extraction includes: to use at 25 DEG C -95 DEG C
The lye of 0.5-30 weight % concentration activates the composite catalyst -72 hours 5 minutes.
16. a kind of composite catalyst of activation, composite catalyst method as described in claims 14 or 15 of the activation
It is made.
17. composite catalyst described in any one of claim 1-10, as described in any one of claim 11-13
Method made from composite catalyst, the composite catalyst obtained activated of method described in claims 14 or 15 and power
Benefit require 16 described at least one of the composite catalyst of activation adding the application in hydrogen or dehydrogenation reaction, it is preferable that
The reaction carries out in fixed bed reactors or moving-burden bed reactor.
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| CN115672345A (en) * | 2022-10-27 | 2023-02-03 | 深圳市飞墨科技有限公司 | Preparation method of single-walled carbon nanotube catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542906A (en) * | 1964-08-16 | 1970-11-24 | Bridgestone Tire Co Ltd | Production of butadiene-styrene graft copolymers with a catalyst containing a nickel complex |
| CN104888808A (en) * | 2014-03-07 | 2015-09-09 | 中国石油化工股份有限公司 | Composite type catalyst and preparation method thereof |
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2017
- 2017-10-25 CN CN201711006229.6A patent/CN109701557B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542906A (en) * | 1964-08-16 | 1970-11-24 | Bridgestone Tire Co Ltd | Production of butadiene-styrene graft copolymers with a catalyst containing a nickel complex |
| CN104888808A (en) * | 2014-03-07 | 2015-09-09 | 中国石油化工股份有限公司 | Composite type catalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115672345A (en) * | 2022-10-27 | 2023-02-03 | 深圳市飞墨科技有限公司 | Preparation method of single-walled carbon nanotube catalyst |
| CN115672345B (en) * | 2022-10-27 | 2023-12-15 | 深圳市飞墨科技有限公司 | Preparation method of single-walled carbon nanotube catalyst |
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