CN107537587A - The processing method of catalyst - Google Patents
The processing method of catalyst Download PDFInfo
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- CN107537587A CN107537587A CN201610498151.3A CN201610498151A CN107537587A CN 107537587 A CN107537587 A CN 107537587A CN 201610498151 A CN201610498151 A CN 201610498151A CN 107537587 A CN107537587 A CN 107537587A
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Abstract
The present invention relates to a kind of processing method of catalyst, it is characterized in that carry out covering charcoal processing using carbohydrate, it is uneven that the technical problems to be solved by the invention are that Pt present in prior art disperses, the easy coking of catalyst, the problem of activity and stability difference, the catalyst and processing method provided, when for dehydrogenating low-carbon alkane or organic liquid hydrogen storage material dehydrogenation reaction, catalyst has Pt decentralization high, carrier is no acidic, course of reaction is substantially without coking, the advantages of active height and high stability, industrial treatment available for dehydrogenation and hydrogenation catalyst.
Description
Technical field
The present invention discloses a kind of processing method of catalyst, more particularly to a kind of dehydrogenation or hydrogenation catalyst
Processing method.
Background technology
As the representative of the sustainable new energy of green, Hydrogen Energy is by extensive concern.At the beginning of 21 century, China and the U.S., Japan, add
Put on airs, European Union etc. has all formulated Hydrogen Energy development plan, try to be the first and carried out correlative study.Hydrogen Energy using include hydrogen prepare, store,
The link such as transport and application, wherein hydrogen energy storage are crucial and difficult points.Hydrogen fuel vehicle is the applicable main path of hydrogen, exploitation
Hydrogen storage technology suitable for hydrogen fuel vehicle is the premise of Hydrogen Energy large-scale application.
At present, hydrogen storage technology mainly has physics hydrogen storage, adsorption hydrogen-storing and chemical hydrogen storage.Physics hydrogen storage technology has met car
Requirement, but its high request and severe operating conditions to equipment make it that contradiction between this technical performance and efficiency is increasingly prominent
Go out.Adsorption hydrogen-storing and chemical hydrogen storage are the emphasis studied at present, achieve certain achievement in research, but will from vehicle-mounted hydrogen storage technology
Seek also certain gap.(organic liquid mainly has organic liquid hydrogen storage technology in chemical hydrogen storage：Hexahydrotoluene, hexamethylene,
Naphthane, decahydronaphthalene, perhydro nitrogen ethyl carbazole, perhydro carbazole etc.) be by catalysis plus, dehydrogenation reversible reaction realize Hydrogen Energy
Storage, the process reaction is reversible, and reactant is recyclable to be recycled, of a relatively high (the about 60-75kg H of hydrogen storage content2/m3, quality
Fraction is 6-8%), meet International Energy Agency and USDOE (DOE) set quota, and grown in the form of organic liquid
Way conveys or can solve the Area distribution problem of non-uniform of the energy, really meets the requirement of Green Chemistry, has stronger application
Prospect.
In organic liquid hydrogen storage technology simultaneously exist hydrogenation and certain embodiments, hydrogenation process is relatively easy, Technical comparing into
Ripe, certain embodiments are highly endothermic, high reversible a reactions, therefore in terms of dynamics and thermodynamics two, high temperature is all
Be advantageous to dehydrogenation reaction progress, but the side reactions such as cracking, carbon distribution easily occur under high temperature can cause the activity of catalyst to reduce even
Inactivation, it is unfavorable for dehydrogenation reaction progress.
Because preparation method is simple and cost is cheap, Pt/Al2O3Catalyst is widely used for as organic liquid hydrogen storage
The dehydrogenation of material, but this catalyst needs high-temperature roasting in preparation process and with hydrogen reducing, is easily caused Pt atoms
Cohesive size, which becomes, ultimately results in greatly active reduction, in addition Al2O3The faintly acid and low specific surface area on surface, during the course of the reaction easily
Generation coking and Pt is set to be not easy to disperse so that the activity and less stable of this catalyst, therefore Pt/Al2O3It is not organic
The preferable dehydrogenation of liquid hydrogen storage material, it is badly in need of carrying out the research of high activity and high stability dehydrogenation.By institute
Have in metal, Pt dehydrogenation effect is best, therefore the emphasis for carrying out the research of organic liquid dehydrogenation is selection specific surface area
Big and weaker or no acidic surface acidity carrier, with the catalyst that this prepares small size Pt and is not easy coking.
Al2O3Mechanical strength is good, and heat endurance is high, cheap, is widely used in petroleum chemical industry, but Al2O3
There is acidic site in surface, be easily broken C-C keys during the course of the reaction, cause catalyst coking, carbon distribution.
Carbon material has good anticoking capability because surface is no acidic, and its specific surface area is big, can be beneficial to scattered
Active component, but carbon material mechanical strength is low, micropore size is small, is used alone to certain difficulty be present as carrier.
If by carbon material and Al2O3It is combined, with carbon material to Al2O3Surface is modified, and is developed excellent with aluminum oxide
Point also has the carrier of carbon material advantage, it would be possible to solves the problems, such as that current organic liquid hydrogen storage material dehydrogenation is present.
CN1193655A discloses a kind of dehydrogenation preparation method for having and covering char combustion aluminium.The patent is with 40-80
γ-the Al of mesh (0.2-0.45mm)2O3It is placed in reactor, volatile hydro carbons is brought to reactor with N2, with 600 DEG C or so
Temperature carry out cracking and cover charcoal obtaining carrier.It is used to be catalyzed cyclohexane dehydrogenation with metals such as this carrier impregnation Pt, Co, Ni, as a result
Show, its activity is than simple γ-Al2O3Carried catalyst improves about 7%-8%.
CN101327454A discloses a kind of modification with core shell structure and covers char combustion alumina supporter and preparation method thereof.Should
Patent is with diameter 1-3mm, length 3-8mm industrial Al2O3For core, Ni, Co, Fe transition metal salt and isopropanol or secondary will be contained
Butanol, which is dissolved in isopropanol or ethanol, is prepared into colloid, and industrial Al is then carried on by way of impregnating or spraying2O3
On core, it is placed in after drying and calcining in reacting furnace, is passed through argon gas, hydrogen gas mixture is reduced to 550-650 DEG C, is then passed to
Carbon source and hydrogen mixed gas are carried out covering charcoal, and modification is obtained after cooling and covers char combustion alumina supporter.Carbon-source gas used be methane,
Ethane or carbon monoxide.In carrier with industrial Al2O3For core, the aluminum oxide for depositing charcoal is shell, available in petrochemical industry process
Hydrotreating.
CN201010559898.8 is disclosed a kind of catalyst for dehydrogen that char combustion alumina supporter is covered based on nanometer and prepares work
Skill, for this method by steps such as gel, hydrolytic precipitation, pre-burning, N2 heat treatments, obtain nanoscale covers charcoal γ-Al2O3Carrier,
Then with the carrier loaded active metal component, the good catalyst of dehydrogenation is obtained after activation.
Above-mentioned patent achieves certain achievement in terms of the activity and stability that improve organic liquid dehydrogenation, but
It is to Al using gas coking method2O3When carrying out covering charcoal, it is based on gas and adsorbs after-condensation knot in aluminum oxide surface acidity position
Jiao, because gas reaches outer surface at first, it is easy in Al2O3Duct coking nearby, duct is blocked, makes its specific surface area big
Amplitude reduction, so as to reduce utilization rate, and patent CN101327454A methods cover charcoal and carried metal simultaneously in preparation process,
Charcoal is likely to cover metal surface, and so as to reduce rate of metal, CN201010559898.8 will cover charcoal process and be applied to
Al2O3Preparation process, be unfavorable for mass producing.
The content of the invention
The technical problems to be solved by the invention are that catalyst activity component decentralization present in prior art is poor, active
The problem of with stability difference, there is provided a kind of processing method of catalyst, the obtained catalyst after this method processing are active
Component high degree of dispersion, carrier are no acidic, avoid the advantages of coking of course of reaction, high activity and high stability.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of processing method of catalyst, it is to carry out covering charcoal processing using carbohydrate.
In above-mentioned technical proposal, it is the load using carbohydrate to catalyst to carry out covering charcoal processing using carbohydrate
Body carries out covering charcoal processing.
In above-mentioned technical proposal, catalyst includes active component and carrier, and carrier provides at portion before charcoal processing is covered
Divide activated centre.
In above-mentioned technical proposal, Carriers Active center is at least partly acid centre.
In above-mentioned technical proposal, carrier does not provide activated centre after covering charcoal processing.
In above-mentioned technical proposal, catalyst is at least one of dehydrogenation, hydrogenation catalyst.
In above-mentioned technical proposal, preferable catalyst is one kind in dehydrogenation, hydrogenation catalyst.
In above-mentioned technical proposal, carbon exists in the form of amorphous carbon after covering charcoal processing.
In above-mentioned technical proposal, cover after charcoal is handled by weight percentage, the content of carbon accounts for the 0.1- of catalyst
10%.
In above-mentioned technical proposal, it is preferred that the content of carbon accounts for the 5-8% of catalyst.
In above-mentioned technical proposal, carrier is selected from aluminum oxide, silica, titanium oxide, magnesia, calcium oxide, cerium oxide and oxygen
Change at least one of zirconium.
In above-mentioned technical proposal, carbohydrate is sucrose, triose, tetrose, pentose, hexose, sugar alcohol, saccharic acid, osamine,
At least one of glucosides.
In above-mentioned technical proposal, it is preferred that carbohydrate is the mixture of sucrose and triose.
In above-mentioned technical proposal, preferable sucrose is 1 with triose mixed proportion:2~2:1.
In above-mentioned technical proposal, the processing method of catalyst comprises the following steps：
(1) carrier is carried out covering charcoal and handles to obtain carbon covered carrier；
(2) active component is introduced in a manner of impregnating or precipitate.
In above-mentioned technical proposal, it is to use carbohydrate solutions impregnated carrier that carrier, which is carried out covering charcoal processing,.
In above-mentioned technical proposal, processing method is obtained again after drying, roasting after using carbohydrate solutions impregnated carrier
To carbon covered carrier.
In above-mentioned technical proposal, processing method is to be calcined to be carried out under the conditions of non-oxygen.
Using technical scheme, to catalyst cover carbon processing, the present invention is only according to carrier and high-area carbon
Property values, then lower roasting is enclosed in non-oxygen atmosphere in carrier surface first by carbohydrate uniform load using dipping/precipitation method
Burn, be made and uniformly cover the alumina support of charcoal, afterwards carried metal again, finally give the good dehydrogenation of active high stability
Or hydrogenation catalyst, achieve good technique effect.
Below by embodiment, the present invention is further elaborated, but the invention is not restricted to following examples.
Embodiment
【Embodiment 1】
Compound concentration is 1% sucrose solution 3mL, weighs 2 grams of shaping Al2O3(determining its water absorption rate as 1.0) adds it
In, 4h is placed, is filtered dry afterwards, is dried 4h in 120 DEG C of baking ovens, be put into N24h is calcined at 550 DEG C in the Muffle furnace of atmosphere, is covered
Char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1 gram to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition is as follows：Pressure normal pressure, 450 DEG C, hydrogen flowing quantity 200mL/min of temperature, reduction
Time is 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, 320 DEG C of temperature, air speed 2h-1, with methyl ring
Representative raw material of the hexane as organic liquid hydrogen storage.It the results are shown in Table 1.
To investigate the stability of catalyst, X2 and X100 is defined, the conversion ratio of raw material when respectively reacting 2h and 100h.
【Embodiment 2】
Compound concentration is 5% sucrose solution 3mL, weighs 2 grams of shaping Al2O3(determining its water absorption rate as 1.0) adds it
In, 4h is placed, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, is put into the Muffle furnace of N2 atmosphere and is calcined 4h at 550 DEG C, covered
Char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is put into vacuum drying chamber afterwards, at 100 DEG C, pressure 0MPa
Lower dry 4h, put it into afterwards in the Muffle furnace of N2 atmosphere and be calcined 4h at 550 DEG C, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 3】
The sucrose and tetrose (sucrose that compound concentration is 5%:Tetrose=3:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 4】
The sucrose and glucosides (sucrose that compound concentration is 5%:Glucosides=3:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 5】
The sucrose and triose (sucrose that compound concentration is 5%:Triose=3:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 6】
Compound concentration is 8% sucrose solution 3mL, weighs 2 grams of shaping Al2O3(determining its water absorption rate as 1.0) adds it
In, 4h is placed, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, is put into the Muffle furnace of N2 atmosphere and is calcined 4h at 550 DEG C, covered
Char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 161.4mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 7】
The sucrose and tetrose (sucrose that compound concentration is 8%:Tetrose=2:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 8】
Compound concentration is 5% triose solution 3mL, weighs 2 grams of shaping Al2O3(determining its water absorption rate as 1.0) adds it
In, 4h is placed, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, is put into the Muffle furnace of N2 atmosphere and is calcined 4h at 580 DEG C, covered
Char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 9】
Compound concentration is 10% glycoside solution 3mL, weighs 2 grams of shaping Al2O3(determining its water absorption rate as 1.0) adds it
In, 4h is placed, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, is put into the Muffle furnace of N2 atmosphere and is calcined 4h at 550 DEG C, covered
Char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 10】
The sucrose and tetrose (sucrose that compound concentration is 5%:Tetrose=2:1) mixed solution 3mL, 2 grams of shaping SiO are weighed2
(determining its water absorption rate as 0.6) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 0.578mL water is added and is configured to solution, 2g is covered into charcoal
Silica supports are added in this solution, and stirring, room temperature places 2h, are dried 4h at 120 DEG C afterwards, are finally put it into N2 atmosphere
4h is calcined at 550 DEG C in the Muffle furnace enclosed, obtains catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 11】
The sucrose and glucosides (sucrose that compound concentration is 5%:Glucosides=2:1) mixed solution 3mL, 2 grams of shaping SiO are weighed2
(determining its water absorption rate as 0.6) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of He atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 0.578mL water is added and is configured to solution, 2g is covered into charcoal
Silica supports are added in this solution, and stirring, room temperature places 2h, are dried 4h at 120 DEG C afterwards, are finally put it into He atmosphere
4h is calcined at 550 DEG C in the Muffle furnace enclosed, obtains catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 12】
The sucrose and triose (sucrose that compound concentration is 5%:Triose=2:1) mixed solution 3mL, 2 grams of shaping TiO are weighed2
(determining its water absorption rate as 0.8) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 0.978mL water is added and is configured to solution, 2g is covered into charcoal
Silica supports are added in this solution, and stirring, room temperature places 2h, are dried 4h at 120 DEG C afterwards, are finally put it into N2 atmosphere
4h is calcined at 550 DEG C in the Muffle furnace enclosed, obtains catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 13】
The sucrose and tetrose (sucrose that compound concentration is 5%:Tetrose=2:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The palladium chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, 2g is covered into charcoal
Alumina support is added in this solution, and stirring, room temperature places 2h, is dried 4h at 120 DEG C afterwards, is finally put it into N2 atmosphere
Muffle furnace in 550 DEG C be calcined 4h, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Embodiment 14】
The sucrose and glucosides (sucrose that compound concentration is 5%:Glucosides=2:1) mixed solution 3mL, 2 grams of shaping Al are weighed2O3
(determining its water absorption rate as 1.0) is added thereto, and places 4h, is filtered dry afterwards, dries 4h in 120 DEG C of baking ovens, be put into the horse of N2 atmosphere
4h not is calcined at 550 DEG C in stove, obtains covering char combustion alumina supporter.
The platinum acid chloride solution that 0.622mL concentration is 161.4mL/L and the KNO3 solution that 0.1mL concentration is 0.1mL/L are taken, is added
Enter 1.378mL water and be configured to solution, 2g is covered into char combustion alumina supporter adds in this solution, and stirring, room temperature places 2h, Zhi Hou
4h is dried at 120 DEG C, finally puts it into the Muffle furnace of N2 atmosphere and is calcined 4h at 550 DEG C, obtain catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Comparative example 1】
Take 0.622ml concentration be 16.14mL/L platinum acid chloride solution, add 1.378mL water be configured to solution, by 2g γ-
Al2O3Add in this solution, stir, room temperature places 2h, is put into vacuum drying chamber afterwards, and at 100 DEG C, pressure is to be dried under 0MPa
4h, then sample is put into Muffle furnace and is calcined 4 hours under the conditions of 550 DEG C, obtain required catalyst.
It is 12-20 mesh that resulting catalyst is ground into granularity, takes 1g to be commented in isotherm formula fixed bed reactors
Valency, evaluates preceding hydrogen reducing, and reducing condition, with embodiment 1, the results are shown in Table 1 with appreciation condition.
【Comparative example 2】
Catalyst is prepared with reference to the method for CN201010559898.8 embodiments 1, resulting catalyst is ground into granulating
Spend for 12-20 mesh, take 1g to be evaluated in isotherm formula fixed bed reactors, evaluate preceding hydrogen reducing, reducing condition is with commenting
Valency condition the results are shown in Table 1 with embodiment 1.
【Comparative example 3】
Catalyst is prepared with reference to the method for CN1193655A embodiments 1, it is 12- that resulting catalyst is ground into granularity
20 mesh, take 1g to be evaluated in isotherm formula fixed bed reactors, evaluate preceding hydrogen reducing, reducing condition is same with appreciation condition
Embodiment 1, the results are shown in Table 1.
Table 1
【Embodiment 15~20】
The catalyst that embodiment 9 is prepared is used for the performance evaluation in dehydrogenating low-carbon alkane producing light olefins, as a result
It is shown in Table 2.
Table 2
【Embodiment 21~26】
The catalyst that embodiment 9 is prepared is used for the performance evaluation of organic liquid hydrogen storage material dehydrogenation reaction, as a result
It is shown in Table 3.
Table 3
【Embodiment 27~30】
The catalyst that embodiment 9 is prepared is used for the performance evaluation that benzene and/or Toluene Hydrogenation react, and the results are shown in Table 4.
Table 4
Claims (18)
1. a kind of processing method of catalyst, it is characterised in that carry out covering charcoal processing using carbohydrate.
2. the processing method of catalyst according to claim 1, it is characterised in that using carbohydrate to catalyst
Carrier carries out covering charcoal processing.
3. the processing method of catalyst according to claim 1, it is characterised in that catalyst includes active component and carrier,
Carrier provides at amount of activated center before charcoal processing is covered.
4. the processing method of catalyst according to claim 3, it is characterised in that activated centre is at least partly in acidity
The heart.
5. the processing method of catalyst according to claim 1, it is characterised in that do not provide activated centre after covering charcoal processing.
6. the processing method of catalyst according to claim 1, it is characterised in that catalyst is dehydrogenation and/or added
Hydrogen catalyst.
7. the processing method of the catalyst according to any one of claim 1~6, it is characterised in that carbon is with nothing after processing
The form of setting carbon is present.
8. the processing method of the catalyst according to any one of claim 1~6, it is characterised in that with weight percent after processing
Than meter, the content of carbon accounts for the 0.1-10% of catalyst.
9. the processing method of catalyst according to claim 8, it is characterised in that after processing by weight percentage, carbon member
The content of element accounts for the 5-8% of catalyst.
10. the processing method of catalyst according to claim 3, it is characterised in that carrier is selected from aluminum oxide, silica, oxygen
Change at least one of titanium, magnesia, calcium oxide, cerium oxide and zirconium oxide.
11. the processing method of catalyst according to claim 1, it is characterised in that carbohydrate be sucrose, triose,
At least one of tetrose, pentose, hexose, sugar alcohol, saccharic acid, osamine and glucosides.
12. the processing method of catalyst according to claim 11, it is characterised in that carbohydrate is selected from sucrose and third
The mixture of sugar, mixed weight ratio are 1:2~2:1.
13. the processing method of catalyst according to claim 1, it is characterised in that processing comprises the following steps：
(1) carrier is carried out covering charcoal and handles to obtain carbon covered carrier；
(2) active component is introduced in a manner of impregnating or precipitate.
14. the processing method of catalyst according to claim 13, it is characterised in that it is to use to carry out covering charcoal processing to carrier
Carbohydrate solutions impregnated carrier.
15. the processing method of catalyst according to claim 14, it is characterised in that impregnated and carried with carbohydrate solutions
Carbon covered carrier is obtained after body after drying, roasting again.
16. the processing method of catalyst according to claim 15, it is characterised in that roasting is carried out under the conditions of non-oxygen.
17. a kind of catalyst, it is characterised in that catalyst is handled through claim 1 methods described.
18. catalyst according to claim 17, it is characterised in that catalyst is hydrogenation catalyst and/or catalysis dehydrogenation
Agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498151.3A CN107537587B (en) | 2016-06-29 | 2016-06-29 | Method for treating catalyst |
Applications Claiming Priority (1)
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| CN113559859A (en) * | 2021-07-23 | 2021-10-29 | 中国地质大学（武汉） | Supported cobalt-based hydrogenation catalyst and preparation method and application thereof |
| US11305263B2 (en) * | 2019-04-30 | 2022-04-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a supported carbon catalyst, supported carbon catalyst and use thereof |
| CN114433222A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation and application thereof |
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