CN107537476A - Dehydrogenation, preparation method and its usage - Google Patents
Dehydrogenation, preparation method and its usage Download PDFInfo
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- CN107537476A CN107537476A CN201610498409.XA CN201610498409A CN107537476A CN 107537476 A CN107537476 A CN 107537476A CN 201610498409 A CN201610498409 A CN 201610498409A CN 107537476 A CN107537476 A CN 107537476A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention discloses a kind of dehydrogenation, preparation method and its usage, including following content：Catalyst is by 0.1~5 part of (a) selected from least one of the race's element of the periodic table of elements the VIIIth metal or its alloy, (b) 1~20 part of carbon, (c) 75~99 parts of carriers compositions；Dehydrogenation is carried out covering charcoal and handles to obtain carbon covered carrier by (a) to carrier, and (b) introduces active component to prepare in a manner of impregnating or precipitate.The technical problems to be solved by the invention are the problem of Pt present in prior art disperse uneven, the easy coking of catalyst, activity and stability difference, dehydrogenation provided and preparation method thereof, when for dehydrogenating low-carbon alkane or organic liquid hydrogen storage material dehydrogenation reaction, catalyst has that Pt decentralization is high, carrier is no acidic, course of reaction is substantially without coking, the advantages of active height and high stability, available in dehydrating alkanes or the commercial Application of organic liquid hydrogen storage material dehydrogenation.
Description
Technical field
The present invention discloses a kind of dehydrogenation, preparation method and its usage, and particularly one kind is used for organic liquid hydrogen storage
Material high stability dehydrogenation catalyst and preparation method thereof.
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, uses N2Volatile hydro carbons is brought to reactor, 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 be Pt present in prior art disperse uneven, the easy coking of catalyst,
Activity and the problem of stability difference, there is provided a kind of dehydrogenation and preparation method thereof, this method be used for dehydrogenating low-carbon alkane or
During organic liquid hydrogen storage material high stability dehydrogenation reaction, catalyst has that Pt high degree of dispersion, carrier are no acidic, avoid reaction
The advantages of coking of process, 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 dehydrogenation, in terms of parts by weight, including following components：
(a) 0.1~5 part is selected from least one of the periodic table of elements group VIII element metal or its alloy；
(b) 1~20 part of carbon；
(c) 75~99 parts of carriers.
In above-mentioned technical proposal, it is preferred that component (a) is selected from least one of platinum metal.
In above-mentioned technical proposal, it is furthermore preferred that component (a) is selected from platinum and/or palladium.
In above-mentioned technical proposal, it is preferred that the content of component (a) is 0.1~3 part.
In above-mentioned technical proposal, it is preferred that in terms of parts by weight, the content of carbon is 1~10 part.
In above-mentioned technical proposal, it is furthermore preferred that in terms of parts by weight, the content of carbon is 5~8 parts.
In above-mentioned technical proposal, it is preferred that carbon exists in the form of amorphous carbon.
In above-mentioned technical proposal, it is preferred that carrier is in aluminum oxide, silica, titanium oxide, magnesia and zirconium oxide
It is at least one.
In above-mentioned technical proposal, it is furthermore preferred that carrier is in aluminum oxide, silica, titanium oxide, magnesia and zirconium oxide
One kind.
In above-mentioned technical proposal, most preferably, carrier is selected from aluminum oxide.
In above-mentioned technical proposal, it is preferred that carbon is introduced by covering charcoal processing.
In above-mentioned technical proposal, it is preferred that the presoma of carbon is carbohydrate.
In above-mentioned technical proposal, it is preferred that the presoma of carbon is first impregnated and/or precipitated, then is dried, is roasted
Carbon covered carrier is obtained after burning.
The preparation method of dehydrogenation in above-mentioned technical proposal, 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 preferred that it is to use carbohydrate solutions impregnated carrier that carrier, which is carried out covering charcoal processing,.
In above-mentioned technical proposal, it is preferred that carbohydrate is sucrose, triose, tetrose, pentose, hexose, sugar alcohol, saccharic acid,
At least one of osamine, glucosides.
In above-mentioned technical proposal, it is preferred that with after carbohydrate solutions impregnated carrier again through drying, roasting after covered
High-area carbon.
In above-mentioned technical proposal, it is preferred that roasting is carried out under the conditions of non-oxygen.
In above-mentioned technical proposal, it is preferred that dry use vacuumizes drying；It is furthermore preferred that processing time is 2-8h, take out true
Reciprocal of duty cycle is -0.1-0MPa, and drying temperature is 80-160 DEG C.
In above-mentioned technical proposal, it is preferred that sintering temperature is 400-650 DEG C, calcination atmosphere N2, Ar, He and H2In extremely
Few one kind.
A kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, propane and/or iso-butane are used as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure of degree, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under the conditions of, raw material and above-mentioned catalyst haptoreaction generation propylene and/or isobutene.
A kind of method of organic liquid hydrogen storage material dehydrogenation, reaction condition are as follows：Reaction pressure is 0~1MPa, temperature is
200~450 DEG C, mass space velocity be 0.1~10h-1；Organic liquid hydrogen storage material produces hydrogen with above-mentioned catalyst haptoreaction
And corresponding aromatic hydrocarbons.
In above-mentioned technical proposal, it is preferred that organic liquid hydrogen storage material is selected from hexahydrotoluene, hexamethylene, naphthane, ten
At least one of hydrogen naphthalene, perhydro nitrogen ethyl carbazole and perhydro carbazole.
In above-mentioned technical proposal, it is preferred that the reaction condition before catalyst reaction is as follows：Reduction temperature is 300-500 DEG C,
It is preferred that 400-500 DEG C, hydrogen flow rate is 100-500mL/min, preferably 200-400mL/min in reduction process, and the recovery time is
2-8h, preferably 3-6h.
For these reasons, the present invention is according to carrier and the peculiar property of high-area carbon, using dipping/precipitation method first by carbon
Hydrate uniform load then encloses lower roasting in carrier surface in non-oxygen atmosphere, and the alumina support for uniformly covering charcoal is made, it
Carried metal again afterwards, finally gives the good dehydrogenation of active high stability.
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 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, 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】
Compound concentration is 9% 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 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】
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 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】
Compound concentration is 20% 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 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 20% 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】
Compound concentration is 5% sugar acid 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 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】
Compound concentration is 10% glycoside solution 3mL, weighs 2 grams of shaping SiO2(determining its water absorption rate as 0.6) 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, 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】
Compound concentration is 10% glycoside solution 3mL, weighs 2 grams of shaping SiO2(determining its water absorption rate as 0.6) 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 He 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, 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】
Compound concentration is 10% glycoside solution 3mL, weighs 2 grams of shaping TiO2(determining its water absorption rate as 0.8) 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, 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】
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 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】
Compound concentration is 20% 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 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 1 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 1 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
Claims (14)
1. a kind of dehydrogenation, in terms of parts by weight, including following components：
(a) 0.1~5 part is selected from least one of the race's element of the periodic table of elements the VIIIth metal or its alloy；
(b) 1~20 part of carbon；
(c) 75~99 parts of carriers.
2. dehydrogenation according to claim 1, it is characterised in that component (a) in platinum metal at least one
Kind.
3. dehydrogenation according to claim 1, it is characterised in that in terms of parts by weight, the content of carbon for 1~
10 parts.
4. the dehydrogenation according to claim 1 or 3, it is characterised in that carbon exists in the form of amorphous carbon.
5. dehydrogenation according to claim 1, it is characterised in that carrier is selected from aluminum oxide, silica, titanium oxide, oxygen
Change at least one of magnesium and zirconium oxide.
6. dehydrogenation according to claim 1, it is characterised in that the presoma of carbon is carbohydrate.
7. the preparation method of the dehydrogenation described in any one of claim 1~6, 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.
8. the preparation method of dehydrogenation according to claim 7, it is characterised in that to carrier cover charcoal and handle is
With carbohydrate solutions impregnated carrier.
9. the preparation method of dehydrogenation according to claim 7, it is characterised in that carbohydrate is sucrose, third
At least one of sugar, tetrose, pentose, hexose, sugar alcohol, saccharic acid, osamine, glucosides.
10. the preparation method of dehydrogenation according to claim 8, it is characterised in that impregnated with carbohydrate solutions
Carbon covered carrier is obtained after carrier after drying, roasting again.
11. the preparation method of dehydrogenation according to claim 10, it is characterised in that roasting is entered under the conditions of non-oxygen
OK.
12. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, propane and/or iso-butane are used as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure of degree, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under the conditions of, raw material and the catalyst haptoreaction generation propylene and/or isobutene described in any one of claim 1~6.
13. a kind of method of organic liquid hydrogen storage material dehydrogenation, reaction condition are as follows：Reaction pressure is 0~1MPa, temperature is
200~450 DEG C, mass space velocity be 0.1~10h-1；Organic liquid hydrogen storage material and the catalysis described in any one of claim 1~6
Agent haptoreaction produces hydrogen and corresponding aromatic hydrocarbons.
14. the method for organic liquid hydrogen storage material dehydrogenation according to claim 13, it is characterised in that organic liquid hydrogen storage
Material is selected from least one of hexahydrotoluene hexamethylene, naphthane, decahydronaphthalene, perhydro nitrogen ethyl carbazole and perhydro carbazole.
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