CN109701610A - Modified dehydrogenation, preparation method and its usage - Google Patents

Modified dehydrogenation, preparation method and its usage Download PDF

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Publication number
CN109701610A
CN109701610A CN201711010828.5A CN201711010828A CN109701610A CN 109701610 A CN109701610 A CN 109701610A CN 201711010828 A CN201711010828 A CN 201711010828A CN 109701610 A CN109701610 A CN 109701610A
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China
Prior art keywords
dehydrogenation
catalyst
modified
mcm
added
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童凤丫
孙清
缪长喜
邵一凡
王仰东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention discloses a kind of modified dehydrogenation, preparation method and its usage, including following content: catalyst is by 0.1~5 part of (a) selected from least one of the VIIIth race's element of the periodic table of elements metal or its alloy, (b) 0.1~3 part selected from least one of subgroup element metallic element or its metal oxide, (c) 92~99 parts of carrier compositions, the technical problems to be solved by the invention are that active component dispersion existing in the prior art is uneven, the easy coking of catalyst, the problem of activity and stability difference, provided dehydrogenation and preparation method thereof, when being used for dehydrogenating low-carbon alkane or organic liquid hydrogen storage material dehydrogenation reaction, the active component dispersion degree of catalyst is high, carrier is no acidic, reaction process is substantially without coking, the active high and high advantage of stability, it can be used for the work of dehydrogenation reaction Industry application.

Description

Modified dehydrogenation, preparation method and its usage
Technical field
The present invention discloses a kind of modified dehydrogenation, preparation method and its usage, especially a kind of to be used for organic liquid Hydrogen storage material high stability dehydrogenation catalyst and preparation method thereof.
Background technique
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., add Japan 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 apply include hydrogen preparation, storage, The links such as transport and application, wherein hydrogen energy storage is crucial and difficult point.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.
Currently, hydrogen storage technology mainly has physics hydrogen storage, adsorption hydrogen-storing and chemical hydrogen storage.Physics hydrogen storage technology has met vehicle Requirement, but it makes the contradiction between this technical performance and efficiency increasingly prominent the high request and severe operating conditions of equipment Out.Adsorption hydrogen-storing and chemical hydrogen storage are the emphasis studied at present, achieve certain research achievement, but want from vehicle-mounted hydrogen storage technology It asks and has a certain gap.In chemical hydrogen storage organic liquid hydrogen storage technology (organic liquid mainly has: 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, relatively high (the about 60-75kg H of hydrogen storage content2/m3, quality Score is 6-8%), meet International Energy Agency and U.S. Department of Energy (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.
Existed simultaneously in organic liquid hydrogen storage technology plus hydrogen and certain embodiments, hydrogenation process is relatively easy, Technical comparing at Ripe, certain embodiments are highly endothermic, high reversible a reactions, therefore in terms of dynamics and thermodynamics two, high temperature is all Be conducive to dehydrogenation reaction progress, but the side reactions such as cracking, carbon distribution easily occur under high temperature and will lead to the activity reduction of catalyst even Inactivation is unfavorable for dehydrogenation reaction progress.
Since preparation method is simple and low in cost, Pt/Al2O3Catalyst is widely used for as organic liquid hydrogen storage The dehydrogenation of material, but this catalyst needs high-temperature roasting and during the preparation process with hydrogen reducing, easily leads to Pt atom Cohesive size, which becomes larger, eventually leads to active reduction, in addition Al2O3The faintly acid and low specific surface area on surface, during the reaction easily Coking occurs and Pt is made to be not easy to disperse, so that the activity and stability of this catalyst are poor, therefore Pt/Al2O3It is not organic The ideal dehydrogenation of liquid hydrogen storage material is badly in need of carrying out the research of high activity and high stability dehydrogenation.By institute Have in metal, the dehydrogenation effect of Pt 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, prepares small size Pt with this and is not easy the catalyst of coking.
CN102247843A discloses a kind of improved method of cycloalkane dehydrogenation Pt base catalyst stability, this method be to Pt/Al2O3Oxide active component CaO, ZrO is added in the carrier of catalyst2、BaO、La2O3、CeO2One of or it is a variety of, Improved catalyst is used for hydrogen storage material cyclohexane dehydrogenation, and activity and stability are all improved.
CN102068990A discloses a kind of catalyst for dehydrogen preparation process that char combustion alumina supporter is covered based on nanometer, this Method by gel, hydrolytic precipitation, pre-burning, N2 heat treatment and etc., 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 Be using carrier be Al2O3, Al2O3The shortcomings that carrier, still remains.Pure silicon molecular sieve such as MCM-41, MCM-42, SBA- 15, SBA-12 large specific surface areas are no acidic, are widely used in catalytic field.
Dezhi Gao etc. uses SBA-15 and MCM-41, for ethyl alcohol gas phase dehydrogenation reaction, to achieve as carrier loaded Cu Preferable effect.(Gao D,Yin H,Wang A,et al.Gas phase dehydrogenation of ethanol using maleic anhydride as hydrogen acceptor over Cu/hydroxylapatite,Cu/SBA- 15,and Cu/MCM-41catalysts[J].Journal of Industrial and Engineering Chemistry, 2015,26:322-332)
Lan Wen wet impregnation simultaneously restores and is prepared for Ru/MCM-41 catalyst, and by this catalyst be used for ammonia borine and Methylamine borane hydrolysis dehydrogenation, the catalyst activity highest when Ru load capacity is 1.12wt%, TOF (transformation frequency) are 288 every point Clock (Wen L, Zheng Z, Luo W, et al.Ruthenium deposited on MCM-41as efficient catalyst for hydrolytic dehydrogenation of ammonia borane and methylamine borane[J].Chinese Chemical Letters,2015,26(11):1345-1350.)
Dong-Jin Kim dry impregnation and reduction are prepared for Pt/MCM-41 and Pt/SBA-15 for denitration reaction, urge Agent is stablized preferable.(Kim D-J,Kim J W,Choung S-J,et al.The catalytic performance of Pt impregnated MCM-41and SBA-15in selective catalytic reduction of NOx[J] .Journal of Industrial and Engineering Chemistry,2008,14(3):308-314.)
When the pure silicons such as MCM-41 and SBA-15 molecular sieve is as carrier, preparation method is substantially with Pt salt direct impregnation point Son sieve, since active force is weaker between the two, Pt is not easy to adsorb over a molecular sieve and disperse, and causes to measure low or Pt size on Pt It is larger.
Summary of the invention
That the technical problem to be solved by the present invention is to dehydrogenation activity existing in the prior art is low, stability is poor and The shortcomings that easy coking, a kind of new dehydrogenation, preparation method and its application method are provided, which is used for lower alkanes When hydrocarbon dehydrogenation prepares low-carbon alkene or organic liquid hydrogen storage material dehydrogenation reaction, have that catalyst activity is high, stability is good and not The advantages of easy coking.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of modified dehydrogenation, based on parts by weight, including following components:
(a) at least one of the VIIIth race's element of the periodic table of elements metal or its alloy are selected from for 0.1~5 part；
(b) at least one of subgroup element metallic element or its metal oxide are selected from for 0.1~3 part；
(c) 92~99 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 0.1~5 part.
In above-mentioned technical proposal, it is preferred that 0.1~2 part of component (b) selected from least one of A race element metallic element Or its metal oxide.
In above-mentioned technical proposal, it is furthermore preferred that component (b) is selected from least one of In, Cs, Ga, Ge, Sr.
In above-mentioned technical proposal, it is preferred that the content of component (b) is 0.1~3 part.
In above-mentioned technical proposal, it is preferred that the processing of carrier via nitride object.
In above-mentioned technical proposal, it is preferred that component (c) is selected from least one of aluminium oxide, silica and molecular sieve.
In above-mentioned technical proposal, it is preferred that carrier is selected from MCM-41, MCM-42, MCM-48, SBA-15, SBA-12, SBA- At least one of 16 and MSU.
The preparation method of modified dehydrogenation in above-mentioned technical proposal, comprising the following steps:
(1) nitrogenate is carried out to carrier to handle to obtain containing nitrogen carriers；
(2) active component is introduced in a manner of impregnating or precipitate；
(3) finished catalyst is obtained through reduction activation component.
In above-mentioned technical proposal, it is preferred that the specific practice with nitrogenous compound processing molecular sieve is: by nitrogenous compound Dissolution in organic solvent, molecular sieve is added, is flowed back 6-24 hours at 60-140 DEG C, evacuated drying process later.
In above-mentioned technical proposal, it is preferred that nitride is selected from tri-n-octyl amine, tri-iso-octylamine, triamido triethoxysilane At least one of with aminopropyl trimethoxysilane.
In above-mentioned technical proposal, it is furthermore preferred that nitride is selected from triamido triethoxysilane, aminopropyl trimethoxy silicon At least one of alkane.
In above-mentioned technical proposal, preferred organic solvent is toluene or ethylene glycol；
In above-mentioned technical proposal, the concentration of preferred nitride in organic solvent is 1-40%；
In above-mentioned technical proposal, the concentration of preferred nitride in organic solvent is 4-10%.
In above-mentioned technical proposal, the concentration of preferred nitride in organic solvent is 6-10%.
In above-mentioned technical proposal, it is preferred that vacuum drying handles the time as 2-8h, and suction is -0.1-0MPa, does Dry temperature is 80-160 DEG C.
In above-mentioned technical proposal, low-temperature reduction processing method are as follows: be 5%-40%'s with concentration at a temperature of 25-80 DEG C Reducing agent solution impregnates catalyst 4-24 hours, and vacuum drying is handled later.
In above-mentioned technical proposal, preferred reduction treatment temperature is 40-80 DEG C, reductant concentration 10%-20%, is impregnated Time is 4-10 hours.
In above-mentioned technical proposal, reducing agent are as follows: sodium borohydride, ethylene glycol, formaldehyde, acetaldehyde, formic acid, in acetic acid etc. at least It is a kind of.
In above-mentioned technical proposal, it is preferred that reducing agent is at least one of sodium borohydride, ethylene glycol.
A kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, uses propane and/or iso-butane for 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 generate 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 and above-mentioned catalyst haptoreaction generate hydrogen 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.
The present invention is according to carrier and the unique property of active metal, especially when carrier selects molecular sieve, using molecule (especially pure silicon molecular sieve) over-assemble organic matter is sieved, one end and the molecular sieve of organic matter link, the other end and active metal salt Stronger binding force can be formed, the salt of active component is anchored on molecular sieve surface, then restore by temperate condition, the amount of obtaining The high high organic liquid hydrogen storage material dehydrogenation of active metal dispersion degree, while selected carrier pure silicon molecular sieve simultaneously Surface is no acidic, can avoid reaction process coking, finally obtains the catalyst of high activity and high stability.
Below by embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiments.
Specific embodiment
[embodiment 1]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 15ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
It is 12-20 mesh that obtained catalyst, which is ground into granularity, is evaluated, is evaluated in isotherm formula fixed bed reactors Condition is as follows: 1 gram of catalyst is fitted into above-mentioned isothermal fixed bed reactors, reaction pressure is normal pressure, and temperature is 320 DEG C, with Representative raw material of the hexahydrotoluene as organic liquid hydrogen storage, air speed 2h-1.The result is shown in tables 1.
For the stability for investigating catalyst, the conversion ratio of catalyst when defining X1 and X100, respectively reaction 1h and 100h.
Examination condition the results are shown in Table 1 with embodiment 1.The coking situation of useless agent is included in table 4 after catalyst operation 100h.
[embodiment 2]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 3]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 33ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 4]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 15ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 10%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 5]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 33ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 10%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 6]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 7]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml N-octyl amine, flow back 6h in 100 DEG C of water-baths, cooling, filtering, and the MCM-41 to be organised after vacuum drying measures its suction Water rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 8]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Octodrine, flow back 6h in 100 DEG C of water-baths, cooling, filtering, and the MCM-41 to be organised after vacuum drying measures its suction Water rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 6.43ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 9]
It weighs 2 grams of molding SBA-15 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, in the ammonia that 19ml is added Propyl trimethoxy silicane, flow back 4h in 100 DEG C of water-baths, cooling, filtering, the SBA- to be organised after vacuum drying 15, measuring its water absorption rate is 5.0.
Taking 6.22mL concentration is the platinum acid chloride solution and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, is added 9.378mL water is configured to solution, and the SBA-15 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into later true Empty drying box, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volumes 20% 4h is restored in NaBH4 solution, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 10]
It weighs 2 grams of molding MCM-42 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the platinum acid chloride solution and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, is added 5.578mL water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into later true Empty drying box, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volumes 20% 4h is restored in NaBH4 solution, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 11]
It weighs 2 grams of molding SBA-15 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the platinum acid chloride solution and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, is added 5.578mL water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into later true Empty drying box, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volumes 20% 4h is restored in NaBH4 solution, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 12]
It weighs 2 grams of molding SBA-16 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Take chloroplatinic acid, 3.21ml/L inidum chloride and 3.21ml/L the strontium chloride mixing that 0.622mL concentration is 16.14mL/L molten Liquid is added 5.578mL water and is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, it After be put into vacuum oven, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of bodies 4h is restored in product 20%NaBH4 solution, later again 100 DEG C in vacuum oven, dry 6h, is made catalysis dehydrogenation under pressure 0MPa Agent.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 13]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.1.
Taking 0.622mL concentration is palladium chloride, 3.21ml/L inidum chloride and the 3.21ml/L strontium chloride of 16.14mL/L, is added 5.578mL water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into later true Empty drying box, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.By this catalyst hydrogen in 450 DEG C of reduction 4h, Dehydrogenation is made.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 14]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 19ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 161.4mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volumes, 10% ethylene glycol water 4h is restored in solution, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 15]
Weigh 2 grams of molding Al2O3It is put into 500ml round-bottomed flask, 300ml toluene is added, in three second of triamido that 33ml is added Oxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the Al to be organised after vacuum drying2O3, measure its suction Water rate is 3.1.
Taking 0.622mL concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 161.4mL/L, and 1.578mL is added Water is configured to solution, the Al that 2g is organised2O3It is added in this solution, stirs, be placed at room temperature for 2h, be put into vacuum oven later, At 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution 4h is restored, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
Examination condition the results are shown in Table 1 with embodiment 1.
[embodiment 16]
Taking 0.622ml concentration is the chloroplatinic acid and 8.03ml/L strontium chloride mixed solution of 16.14mL/L, and 1.378mL is added Water is configured to solution, by 2g γ-Al2O3It is added in this solution, stirs, be placed at room temperature for 2h, be put into vacuum oven later, 100 DEG C, pressure is dry 4h under 0MPa, then sample is put into Muffle furnace and is roasted 4 hours under the conditions of 550 DEG C, obtains required urge Agent.
It is 12-20 mesh that obtained catalyst, which is ground into granularity, is evaluated, is evaluated in isotherm formula fixed bed reactors Preceding to use hydrogen reducing, reducing condition is as follows, and pressure is normal pressure, and temperature is 450 DEG C, hydrogen flowing quantity 200mL/min, the recovery time For 4h, cooling evaluation later checks and rates condition with embodiment 1, the results are shown in Table 1.Catalyst runs the coking situation of useless agent after 100h It is included in table 4.
[embodiment 17]
Taking 0.622ml concentration is the chloroplatinic acid and 8.03ml/L inidum chloride mixed solution of 16.14mL/L, and 1.378mL is added Water is configured to solution, by 2g γ-Al2O3It is added in this solution, stirs, be placed at room temperature for 2h, be put into vacuum oven later, 100 DEG C, pressure is dry 4h under 0MPa, then sample is put into Muffle furnace and is roasted 4 hours under the conditions of 550 DEG C, obtains required urge Agent.
It is 12-20 mesh that obtained catalyst, which is ground into granularity, is evaluated, is evaluated in isotherm formula fixed bed reactors Preceding to use hydrogen reducing, reducing condition is as follows, and pressure is normal pressure, and temperature is 450 DEG C, hydrogen flowing quantity 200mL/min, the recovery time For 4h, cooling evaluation later checks and rates condition with embodiment 1, the results are shown in Table 1.Catalyst runs the coking situation of useless agent after 100h It is included in table 4.
[comparative example 1]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 15ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the chloroplatinic acid and 1.61ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
It is 12-20 mesh that obtained catalyst, which is ground into granularity, is evaluated, is evaluated in isotherm formula fixed bed reactors Condition is as follows: 1 gram of catalyst is fitted into above-mentioned isothermal fixed bed reactors, reaction pressure is normal pressure, and temperature is 320 DEG C, with Representative raw material of the hexahydrotoluene as organic liquid hydrogen storage, air speed 2h-1.The result is shown in tables 1.
For the stability for investigating catalyst, the conversion ratio of catalyst when defining X2 and X100, respectively reaction 2h and 100h.
Examination condition the results are shown in Table 1 with embodiment 1.The coking situation of useless agent is included in table 4 after catalyst operation 100h.
[comparative example 2]
It weighs 2 grams of molding MCM-41 molecular sieves and is put into 500ml round-bottomed flask, 300ml toluene is added, be added the three of 15ml Amino triethoxysilane, flow back 6h in 100 DEG C of water-baths, cooling, filtering, the MCM- to be organised after vacuum drying 41, measuring its water absorption rate is 3.0.
Taking 0.622mL concentration is the chloroplatinic acid and 160.6ml/L inidum chloride mixed solution of 16.14mL/L, and 5.578mL is added Water is configured to solution, and the MCM-41 that 2g is organised is added in this solution, and stirring is placed at room temperature for 2h, is put into vacuum drying later Case, at 100 DEG C, pressure is dry 4h under 0MPa, obtains catalyst.This catalyst is put into 1.5 times of volume 20%NaBH4 solution Middle reduction 4h, later again 100 DEG C in vacuum oven, dry 6h, is made dehydrogenation under pressure 0MPa.
It is 12-20 mesh that obtained catalyst, which is ground into granularity, is evaluated, is evaluated in isotherm formula fixed bed reactors Condition is as follows: 1 gram of catalyst is fitted into above-mentioned isothermal fixed bed reactors, reaction pressure is normal pressure, and temperature is 320 DEG C, with Representative raw material of the hexahydrotoluene as organic liquid hydrogen storage, air speed 2h-1.The result is shown in tables 1.
For the stability for investigating catalyst, the conversion ratio of catalyst when defining X2 and X100, respectively reaction 2h and 100h.
Examination condition the results are shown in Table 1 with embodiment 1.The coking situation of useless agent is included in table 4 after catalyst operation 100h.
Examination condition the results are shown in Table 1 with embodiment 1.
Table 1
Note: 4.8%* indicates that the concentration of nitride in organic solvent is 4.8%, similarly hereinafter.
[embodiment 18~23]
The catalyst that embodiment 2 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 24~30]
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
Table 4

Claims (15)

1. a kind of modified dehydrogenation, based on parts by weight, including following components:
(a) at least one of the VIIIth race's element of the periodic table of elements metal or its alloy are selected from for 0.1~5 part；
(b) 0.1~3 part selected from least one of subgroup element metallic element or its metal oxide；
(c) 92~99 parts of carriers.
2. modified dehydrogenation according to claim 1, it is characterised in that component (a) is selected from one of platinum metal Or it is at least one.
3. modified dehydrogenation according to claim 1, it is characterised in that component is it is characterized in that component (b) is selected from One of In, Cs, Ga, Ge, Sr or at least one.
4. modified dehydrogenation according to claim 1, it is characterised in that component (c) carrier is selected from aluminium oxide, oxidation One of silicon and molecular sieve are at least one.
5. modified dehydrogenation according to claim 1 or 4, it is characterised in that carrier is selected from pure silicon molecular sieve MCM- 41, one of MCM-42, MCM-48, SBA-15, SBA-12, SBA-16 and MSU or at least one.
6. according to modification dehydrogenation described in right 1, it is characterised in that carrier is modified by nitrogen.
7. the preparation method of the described in any item modified dehydrogenations of Claims 1 to 5, comprising the following steps:
(1) nitrogenate is carried out to carrier to handle to obtain containing nitrogen carriers；
(2) active component is introduced in a manner of impregnating or precipitate；
(3) finished catalyst is obtained through reduction activation component.
8. being modified the preparation method of dehydrogenation according to claim 6, it is characterised in that handled and divided with nitrogenous compound The specific practice of son sieve is: in organic solvent by nitrogenous compound dissolution, then molecular sieve being added, next time at 60-140 DEG C Stream is after 6-24 hours, then evacuated drying process.
9. being modified the preparation method of dehydrogenation according to claim 6, it is characterised in that it is just pungent that nitrogenate is selected from three One of amine, tri-iso-octylamine, triamido triethoxysilane and aminopropyl trimethoxysilane are at least one.
10. being modified the preparation method of dehydrogenation according to claim 7, it is characterised in that vacuum drying handles the time For 2-8 hours and/or suction is -0.1-0MPa and/or drying temperature is 80-160 DEG C.
11. the preparation method of dehydrogenation according to claim 6, it is characterised in that the condition of reduction treatment are as follows: in 25- At a temperature of 80 DEG C, impregnated catalyst 4-24 hours with the reducing agent solution that mass concentration is 5%-40%, vacuum drying later Processing.
12. the preparation method of dehydrogenation according to claim 9, it is characterised in that reducing agent is selected from sodium borohydride, second One of glycol, formaldehyde, acetaldehyde, formic acid and acetic acid are at least one.
13. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene uses propane and/or iso-butane for 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 described in any item modified dehydrogenation haptoreactions of Claims 1 to 5 generate propylene and/or isobutyl Alkene.
14. 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 described in any item modifications of Claims 1 to 5 Dehydrogenation haptoreaction generates hydrogen and corresponding aromatic hydrocarbons.
15. the method for organic liquid hydrogen storage material dehydrogenation according to claim 12, it is characterised in that organic liquid hydrogen storage Material is selected from one of hexahydrotoluene hexamethylene, naphthane, decahydronaphthalene, perhydro nitrogen ethyl carbazole and perhydro carbazole or at least It is a kind of.
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CN112701301A (en) * 2019-10-23 2021-04-23 中国石油化工股份有限公司 Coating material, preparation method and application thereof, fuel cell electrode and fuel cell
CN113509950A (en) * 2021-04-28 2021-10-19 福州大学 Preparation method of gallium-based catalyst taking alumina modified by non-metallic elements as carrier
CN115805073A (en) * 2021-09-13 2023-03-17 中国石油化工股份有限公司 Dehydrogenation catalyst, preparation method and application thereof, and method for preparing hydrogen by virtue of dehydrogenation of methylcyclohexane

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Publication number Priority date Publication date Assignee Title
CN111892018A (en) * 2019-05-06 2020-11-06 中国石油化工股份有限公司 Method for providing high purity hydrogen
CN112701301A (en) * 2019-10-23 2021-04-23 中国石油化工股份有限公司 Coating material, preparation method and application thereof, fuel cell electrode and fuel cell
CN112701301B (en) * 2019-10-23 2022-12-09 中国石油化工股份有限公司 Coating material, preparation method and application thereof, fuel cell electrode and fuel cell
CN113509950A (en) * 2021-04-28 2021-10-19 福州大学 Preparation method of gallium-based catalyst taking alumina modified by non-metallic elements as carrier
CN115805073A (en) * 2021-09-13 2023-03-17 中国石油化工股份有限公司 Dehydrogenation catalyst, preparation method and application thereof, and method for preparing hydrogen by virtue of dehydrogenation of methylcyclohexane

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