CN110075855A - A kind of dehydrogenation and its preparation method and application - Google Patents
A kind of dehydrogenation and its preparation method and application Download PDFInfo
- Publication number
- CN110075855A CN110075855A CN201910408652.1A CN201910408652A CN110075855A CN 110075855 A CN110075855 A CN 110075855A CN 201910408652 A CN201910408652 A CN 201910408652A CN 110075855 A CN110075855 A CN 110075855A
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- Prior art keywords
- dehydrogenation
- roasting
- time
- drying
- temperature
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 62
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- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 275
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 268
- 238000007598 dipping method Methods 0.000 claims description 123
- 238000003756 stirring Methods 0.000 claims description 123
- 238000001035 drying Methods 0.000 claims description 118
- 229910052697 platinum Inorganic materials 0.000 claims description 75
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 69
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- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 46
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- 229910052746 lanthanum Inorganic materials 0.000 description 11
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- 230000000052 comparative effect Effects 0.000 description 10
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 239000001294 propane Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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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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- Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of dehydrogenation, dehydrogenation is using modified aluminas as carrier, using Pt as active component, using perovskite containing Ga as auxiliary agent；The mass percentage that the mass percentage of Pt is 0.1%~0.5%, Ga in dehydrogenation is 0.4%~3.1%.In addition, preparation method of the invention is simple the present invention also provides a kind of method for preparing above-mentioned dehydrogenation and application of the catalyst in dehydrating alkanes alkene, the dehydrogenation using preparation method preparation has high catalytic performance in dehydrating alkanes；Dehydrogenation of the invention has high catalyst activity, anti-carbon and the characteristic having good stability, and preparation method is simply easy to accomplish, is with a wide range of applications.
Description
Technical field
The invention belongs to dehydrogenation technical fields, and in particular to a kind of dehydrogenation and preparation method thereof and answer
With.
Background technique
Dehydrogenation is mainly used for dehydrogenating propane and generates propylene, butane dehydrogenation generation butadiene or ethylbenzene dehydrogenation generation benzene
Ethylene, propylene are polyacrylic raw material, and butadiene is the raw material of synthetic rubber or acrylic fibers, and styrene is the raw material of synthetic resin.
Dehydrogenation reaction is that a kind of reaction process is reversible, absorbs heat, the increased reaction of molecular number, and the condition of high temperature and low pressure is more advantageous to reaction
Progress.Currently, dehydrogenation reaction will usually carry out under the conditions of 300 DEG C~900 DEG C of temperature, reaction process with side reaction,
Current common dehydrogenation is easy carbon distribution and reduces the service life.Suitable dehydrogenation can promote dehydrogenation reaction to
Target direction carries out, and reaction selectivity is to investigate the important indicator of dehydrogenation.
Selecting suitable dehydrogenation is the key that improve dehydrogenation reaction rate and selectivity, suitable dehydrogenation
It should have the following characteristics that
(1) heat-resist and power of regeneration is strong, has the ability not being sintered in the high temperature environment；
(2) chemical stability is good, has the ability of anti-hydrogen reducing and water vapor encroachment under high temperature environment；
Common dehydrogenation is mainly support type (such as platinum, copper, silver, nickel) and metal oxide (such as chromium oxide, oxidation
Iron, zinc oxide, magnesia) catalyst.Dehydrogenation has higher requirement to thermal stability, due to generating during coke regeneration
High reaction temperature and heat be easy to make catalyst to generate thermal deformation and structure sintering, cause carbon distribution generation to eventually lead to catalyst
Inactivation reduces catalytic perfomance.Therefore, the dehydrogenation that a kind of structure thermal stability is strong, selectivity is high and reactivity is strong is studied
Catalyst seems most important.
As the important component in dehydrogenation family, mainly with Al2O3、SiO2, molecular sieve etc. be carrier,
It is the platinum group catalyst of main active component by people's extensive concern using platinum.Patent No. US7375049, the day for announcing 2008
In on May 20, in, ethane dehydrogenation platinum based catalyst is disclosed in united states patent in entitled " CATALYST catalyst ", the catalysis
Agent is relatively stable in initial stage activity, catalyst deuterogenesis carbon distribution and sintering phenomenon.Patent No. US6756515, bulletin
Day is on June 29th, 2004, entitled " Dehydrogenation Process Using Layered Catalyst
The dehydrogenating technology of Composition layered catalyst component " platinum base γ-Al is disclosed in united states patent2O3Dehydrogenation,
In reaction process, the γ-Al of the catalyst2O3Side reaction is more at the acidic site of carrier surface, meanwhile, occur during reaction
The change of apparent crystallinity and specific surface area, the reason for this is that under hot conditions carrier structure unstability and certain embodiments
The carbon distribution of middle generation.Application No. is 871015137, publication date is on October 12nd, 1988, and entitled " dehydrogen of saturated hydrocarbon is used
Platinum, tin, lithium, sulfur catalyst " Chinese patent disclosure in disclose a kind of saturated hydrocarbons dehydrogenation, use is coprecipitated
Shallow lake method prepares alumina globule, loading platinum, and there are specific surface areas that lower, load noble metal is easy to for the carrier of the catalyst
The deficiencies of loss.Researching and developing has macropore, high activity, highly selective and anti-carbon and the stable catalyst of sintering character extremely
It closes important.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of dehydrogenation
And its preparation method and application.The dehydrogenation has efficient catalysis dehydrogenation performance；Preparation method is simple, using the preparation
The dehydrogenation of method preparation has high catalytic performance in dehydrating alkanes；Dehydrogenation of the invention and its preparation side
Method and application have high catalyst activity, anti-carbon and the characteristic having good stability, and preparation method is simply easy to accomplish, have wide
General application prospect.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of dehydrogenation, which is characterized in that
The dehydrogenation is using modified aluminas as carrier, using Pt as active component, using perovskite containing Ga as auxiliary agent；The dehydrogenation is urged
The mass percentage that the mass percentage of Pt is 0.1%~0.5%, Ga in agent is 0.4%~3.1%.
Above-mentioned a kind of dehydrogenation, which is characterized in that the molecular formula of the perovskite containing Ga is LaxSr1-xCoyGa1- yO3, 0.1≤x≤0.9,0.1≤y≤0.9.
A kind of above-mentioned dehydrogenation, which is characterized in that the preparation method of the perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continue plus lye to pH be 9.0~10.5, before obtaining perovskite containing Ga
Drive body；The lye is the ammonium hydroxide that mass concentration is 10%~20%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and nitre
Sour gallium；
Step 2: obtaining the presoma of perovskite containing Ga described in step 1 successively by drying, roasting and grinding containing Ga
Perovskite；The temperature of the drying is 90 DEG C~110 DEG C, and the time of drying is 10h~15h；The atmosphere of the roasting is air
Atmosphere, the temperature of roasting are 800 DEG C~1000 DEG C, and the time of roasting is 5h~10h；The partial size of the perovskite containing Ga is 200
Mesh~300 mesh.
A kind of above-mentioned dehydrogenation, which is characterized in that the average pore size of the dehydrogenation be 95nm~
325nm；The pore volume of the dehydrogenation is 1.2mL/g~1.7mL/g；The specific surface area of the dehydrogenation is
260m2/ g~390m2/g。
Above-mentioned a kind of dehydrogenation, which is characterized in that the mass percentage of Ga is in the dehydrogenation
1.1%~3.1%.
In addition, the present invention also provides a kind of methods for preparing above-mentioned dehydrogenation, which is characterized in that including following step
It is rapid:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, it is dry after being stirred at room temperature, it obtains
To modified aluminas；
Step 3: being stirred dipping to modified aluminas described in step 2 with platinum acid chloride solution, obtain dipping Pt's
Modified chlorinated aluminium；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged at room temperature, by the leaching after ageing
Then the modified chlorinated aluminium of stain Pt is dried in 70 DEG C~80 DEG C solvent evaporateds, roast, and grinding obtains the modified oxidized of supporting Pt
Aluminium；
Step 5: perovskite containing Ga is uniformly mixed with the modified aluminas of supporting Pt described in step 4, after forming
Obtain dehydrogenation.
Above-mentioned method, which is characterized in that the mass concentration of dust technology described in step 1 is 4%~8%, dust technology
Quality is 4 times~8 times of the quality of aluminium oxide；Pretreated temperature described in step 1 is 80 DEG C~110 DEG C, when pretreated
Between be 0.5h~2h；The temperature of drying described in step 1 is 80 DEG C~150 DEG C, and the time of drying is 3h~10h；In step 1
The temperature of the roasting is 300 DEG C~400 DEG C, and the time of roasting is 3h~6h；
The mass concentration of modifying agent is 5%~15% in modifier solution described in step 2, and the modifying agent is carbonic acid
One or more of sodium, potassium carbonate, sodium acetate and sodium citrate；The quality of modifier solution described in step 2 is pretreatment
3 times~6 times of quality of aluminium oxide；The time of stirring described in step 2 is 30min~90min.
Above-mentioned method, which is characterized in that the method for dipping is stirred described in step 3 are as follows: be added to modified aluminas
Mass concentration is in the platinum acid chloride solution of 0.01g/mL~0.03g/mL, and it is 9~11 that lye, which is added dropwise, and adjusts pH, at 40 DEG C~70 DEG C
Under the conditions of stirring dipping 5h~8h after, remove residul liquid-removing, obtain for the first time stir dipping after modified aluminas；First time is stirred
Modified aluminas after dipping is added in the platinum acid chloride solution that mass concentration is 0.01g/mL~0.03g/mL, and lye tune is added dropwise
Saving pH is 9~11, under the conditions of 40 DEG C~70 DEG C after stirring dipping 5h~8h, removes residul liquid-removing, obtains the modified chlorinated of dipping Pt
Aluminium；The lye is the ammonium hydroxide that mass concentration is 5%~10%.
Above-mentioned method, which is characterized in that the time of ageing described in step 4 is 5h~10h；It is dried described in step 4
Dry temperature is 110 DEG C~130 DEG C, and the time of drying is 10h~15h；The atmosphere of roasting described in step 4 is air atmosphere,
The temperature of roasting is 400 DEG C~600 DEG C, and the time of roasting is 4h~6h；The modified aluminas of supporting Pt described in step 4
Partial size is 200 mesh~300 mesh；Molding described in step 5 includes granulating and forming, pelletizing molding or integrally formed.
Further, the application the present invention also provides a kind of above-mentioned dehydrogenation in dehydrating alkanes alkene.
Compared with the prior art, the present invention has the following advantages:
1, dehydrogenation of the invention with the dehydrogenation with modified aluminas be carrier loaded active component Pt, with
Perovskite containing Ga is auxiliary agent, and the mass percentage of Pt is the mass percentage of 0.1%~0.5%, Ga in dehydrogenation
It is 0.4%~3.1%；Pt disperses as active component in modified aluminas apparent height, has high reactivity, calcium containing Ga
Titanium ore Lacking oxygen abundant can further promote the dispersion of surface active composition, and collaboration promotes catalytic dehydrogenation, which urges
Agent has high alkane conversion ratio and olefine selective, high anti-carbon and caking power, high suppression in carrying out dehydrogenation reaction process
Brewed brine element poisoning capability and service life, reactivity still with higher after dehydrogenation activation.
2, dehydrogenation of the invention carries out table to alumina catalyst support by dust technology using modified aluminas as carrier
Face is modified, so that carrier surface is had oxygen-containing functional group abundant, increases average specific surface area, the hole Kong Rongyu of alumina catalyst support
Diameter can effectively be anchored metal, adsorbed hydrogen；Modified aluminas is conducive to uniformly dividing for metal when carrying out metal impregnation
Dissipate and the interaction of metal and modified aluminas, when carrying out catalytic dehydrogenating reaction, be conducive to the absorption of reactant molecule with
The desorption of product molecule, while can effectively reduce the generation of carbon distribution.
It is 3, of the invention preferably using one or more of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate as modifying agent,
Average specific surface area, the aperture Kong Rongyu of alumina support can effectively be enhanced, enrich carrier surface oxygen-containing functional group and
Basic sites improve the conversion ratio of dehydrating alkanes reaction.
4, the present invention obtains the modified chlorinated aluminium of supporting Pt using stirring dipping, is lived twice to modified chlorinated alumina supporter
The dipping process of property component, to ensure active component thorough impregnation in the fine dispersion on carrier, realizing active component.
5, the present invention can promote gallium element to introduce dehydrogenation, perovskite containing gallium using perovskite containing gallium as auxiliary agent
As a kind of oxygen exchange material of good performance, Lacking oxygen abundant can cooperate with promotion catalytic dehydrogenation, meanwhile, calcium containing gallium
Titanium ore in anti-carbon and is sintered to dehydrogenation and has good facilitation in terms of inhibiting halogen；The present invention
Perovskite containing gallium be prepared using coprecipitation, preparation method is simple, easily operated.
6, dehydrogenation preparation process of the invention is simple, is easy to produce in enormous quantities, production cost is low.
Below with reference to embodiment and attached drawing, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is the XRD diagram of the perovskite containing Ga prepared in the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 90 DEG C, and the time of drying is 10h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 800 DEG C, and the time of roasting is 5h；The partial size of the perovskite containing Ga is
200 mesh.
The XRD spectra of the perovskite containing Ga prepared by the present embodiment as shown in Figure 1, the position of diffraction maximum be 23.2 °,
32.9 °, 40.6 °, 47.4 °, 58.8 °, 68.9 ° and 78.6 °, with LaCoO3Standard card PDF48-0123 matching；Due to Sr, Ga
Doping, the peak position relative standard of the diffraction bee of the perovskite containing Ga block to the movement of low angle direction, show Sr, Ga, La, Co and be stored in
In the crystal structure of perovskite.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 4%, and the quality of the dust technology is the 4 of the quality of aluminium oxide
Times；The pretreated temperature is 80 DEG C, and the pretreated time is 0.5h；The temperature of the drying is 80 DEG C, the time of drying
For 10h；The temperature of roasting is 300 DEG C, and the time of roasting is 3h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 5% in the modifier solution, and the modifying agent is carbonic acid
Sodium, or it is two or more in sodium carbonate, potassium carbonate, sodium acetate and sodium citrate, or be potassium carbonate, sodium acetate or lemon
Lemon acid sodium；The time of the stirring is 30min；The quality of the modifier solution is 6 times of the quality of pretreated aluminium oxide；
Step 3: being 0.1% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.01g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 9, under the conditions of 40 DEG C stirring dipping 5h after, remove residul liquid-removing, obtain for the first time
Modified aluminas after stirring dipping；It is 0.01g/mL that modified aluminas after first time stirring dipping, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 9, under the conditions of 40 DEG C stirring dipping 5h after, remove residul liquid-removing, obtain dipping Pt
Modified chlorinated aluminium；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates the volume of platinum acid chloride solution used
Than for 1:1；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 70 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 200 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 5h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 500 DEG C, and the time of roasting is 4h；
Step 5: according to mass ratio being 1:7's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The macropore that the dehydrogenation is average pore size 95nm is de-
Hydrogen catalyst, specific surface area 263m2/ g, pore volume 1.22mL/g.
Embodiment 2
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 10.5, obtain the presoma of perovskite containing Ga；
The lye is the ammonium hydroxide that mass concentration is 20%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitre
The ratio between amount of substance of sour lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 110 DEG C, and the time of drying is 15h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 1000 DEG C, and the time of roasting is 10h；The partial size of the perovskite containing Ga
For 300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 8%, and the quality of the dust technology is the 8 of the quality of aluminium oxide
Times；The pretreated temperature is 110 DEG C, and the pretreated time is 2h；The temperature of the drying is 90 DEG C；The time of drying is
8h；The temperature of roasting is 400 DEG C, and the time of roasting is 6h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 15% in the modifier solution, and the modifying agent is quality
Than the sodium carbonate and potassium carbonate for 1:1, or one of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate, three kinds or
Four kinds, be perhaps that sodium carbonate and sodium acetate are perhaps sodium carbonate and sodium citrate or are potassium carbonate and sodium acetate, Huo Zhewei
Potassium carbonate and sodium citrate, or be sodium acetate and sodium citrate；The time of the stirring is 90min；The modifier solution
Quality be 3 times of quality of pretreated aluminium oxide；
Step 3: being 0.1% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 11, under the conditions of 70 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 11 that lye, which is added dropwise, and adjusts pH, under the conditions of 70 DEG C after stirring dipping 8h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 10h；The temperature of the drying is 130 DEG C, and the time of drying is 15h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 600 DEG C, and the time of roasting is 6h；
Step 5: according to mass ratio being 1:18's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 120nm
Dehydrogenation, specific surface area 329m2/ g, pore volume 1.52mL/g.
Embodiment 3
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.5, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 15%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
250 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 100 DEG C；The time of drying
For 6h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is quality
Than for the sodium carbonate of 1:1:2:1, potassium carbonate, sodium acetate and sodium citrate, or sodium carbonate, potassium carbonate, sodium acetate and lemon
One of lemon acid sodium, two or three；The time of the stirring is 60min；The quality of the modifier solution is pretreatment
5 times of quality of aluminium oxide；
Step 3: being 0.1% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 70 DEG C after stirring dipping 8h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 10%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 250 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 200nm
Dehydrogenation, specific surface area 358m2/ g, pore volume 1.37mL/g.
Embodiment 4
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 10.0, obtain the presoma of perovskite containing Ga；
The lye is the ammonium hydroxide that mass concentration is 15%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitre
The ratio between amount of substance of sour lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 110 DEG C；The time of drying
For 5h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 5 times of the quality of pretreated aluminium oxide；
Step 3: being 0.5% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 6h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 230nm
Dehydrogenation, specific surface area 374m2/ g, pore volume 1.67mL/g.
Embodiment 5
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 120 DEG C；The time of drying
For 5h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 5 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 6h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 300nm
Dehydrogenation, specific surface area 389m2/ g, pore volume 1.71mL/g.
Embodiment 6
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
200 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 90 DEG C, and the pretreated time is 1h；The temperature of the drying is 130 DEG C；The time of drying is
4h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 4 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.03g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.03g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 8h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 200 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 500 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after pelletizing forms；The dehydrogenation is the macropore that average pore size is 325nm
Dehydrogenation, specific surface area 365m2/ g, pore volume 1.57mL/g.
Embodiment 7
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 20%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 6h；The partial size of the perovskite containing Ga is
300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 140 DEG C；The time of drying
For 4h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is acetic acid
Sodium；The time of the stirring is 60min；The quality of the modifier solution is 4 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.01g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 9, under the conditions of 50 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain for the first time
Modified aluminas after stirring dipping；It is 0.01g/mL that modified aluminas after first time stirring dipping, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 9, under the conditions of 50 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain dipping Pt
Modified chlorinated aluminium；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates the volume of platinum acid chloride solution used
Than for 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 400 DEG C, and the time of roasting is 4h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after pelletizing forms；The dehydrogenation is the macropore that average pore size is 280nm
Dehydrogenation, specific surface area 344m2/ g, pore volume 1.48mL/g.
Embodiment 8
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 6h；The partial size of the perovskite containing Ga is
250 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 90 DEG C, and the pretreated time is 1h；The temperature of the drying is 150 DEG C；The time of drying is
3h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is acetic acid
Sodium；The time of the stirring is 60min；The quality of the modifier solution is 4 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.01g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 50 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.01g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 50 DEG C after stirring dipping 8h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 10%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 250 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 400 DEG C, and the time of roasting is 4h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after pelletizing forms；The dehydrogenation is the macropore that average pore size is 270nm
Dehydrogenation, specific surface area 286m2/ g, pore volume 1.63mL/g.
Embodiment 9
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0, obtain the presoma of perovskite containing Ga；Institute
Stating lye is the ammonium hydroxide that mass concentration is 15%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitric acid
The ratio between amount of substance of lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 5:5:3:7；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.5Sr0.5Co0.3Ga0.7O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 2h；The temperature of the drying is 130 DEG C；The time of drying
For 4h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 5 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 6h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:14's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after integrally formed；The dehydrogenation is the macropore that average pore size is 230nm
Dehydrogenation, specific surface area 294m2/ g, pore volume 1.58mL/g.
Embodiment 10
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 10.0, obtain the presoma of perovskite containing Ga；
The lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitre
The ratio between amount of substance of sour lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 9:1:1:9；
Step 2: grinding obtains molecule by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Formula is La0.9Sr0.1Co0.1Ga0.9O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；It is described
The atmosphere of roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The partial size of the perovskite containing Ga is
300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 120 DEG C；The time of drying
For 5h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 5 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 6h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:7's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 318nm
Dehydrogenation, specific surface area 370m2/ g, pore volume 1.60mL/g.
Embodiment 11
Prepare perovskite containing Ga the following steps are included:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 10.0, obtain the presoma of perovskite containing Ga；
The lye is the ammonium hydroxide that mass concentration is 10%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, the nitre
The ratio between amount of substance of sour lanthanum, strontium nitrate, cobalt nitrate and gallium nitrate is 1:9:9:1；
Step 2: grinding is obtained by the presoma of perovskite containing Ga described in step 1 successively by drying, roasting
Molecular formula is La0.1Sr0.9Co0.9Ga0.1O3Perovskite containing Ga；The temperature of the drying is 100 DEG C, and the time of drying is 12h；
The atmosphere of the roasting is air atmosphere, and the temperature of roasting is 900 DEG C, and the time of roasting is 8h；The grain of the perovskite containing Ga
Diameter is 300 mesh.
The method for preparing dehydrogenation, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 6%, and the quality of the dust technology is the 5 of the quality of aluminium oxide
Times；The pretreated temperature is 100 DEG C, and the pretreated time is 1h；The temperature of the drying is 120 DEG C；The time of drying
For 5h；The temperature of roasting is 350 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 5 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.02g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 60 DEG C stirring dipping 6h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.02g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 60 DEG C after stirring dipping 6h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 8%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, be ground to partial size be 300 mesh, obtain supporting Pt
Modified aluminas；The time of the ageing is 8h；The temperature of the drying is 120 DEG C, and the time of drying is 10h；The roasting
The atmosphere of burning is air atmosphere, and the temperature of roasting is 550 DEG C, and the time of roasting is 5h；
Step 5: according to mass ratio being 1:7's by the modified aluminas of supporting Pt described in perovskite containing Ga and step 4
Ratio uniform mixing, obtains dehydrogenation after granulating and forming；The dehydrogenation is the macropore that average pore size is 293nm
Dehydrogenation, specific surface area 1.54m2/ g, pore volume 335mL/g.
Comparative example 1
The method for preparing dehydrogenation of this comparative example, comprising the following steps:
Step 1: aluminium oxide is dried, roasts, obtain pretreated aluminium oxide；The temperature of the drying is 130 DEG C；It dries
The dry time is 4h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: be 0.3% according to the mass percentage of Pt in dehydrogenation, it will be pretreated described in step 1
Aluminium oxide is added in the platinum acid chloride solution that mass concentration is 0.03g/mL, and it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 50 DEG C
After stirring dipping 8h, residul liquid-removing is removed, the aluminium chloride of dipping Pt is obtained；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 3: the aluminium chloride for impregnating Pt described in step 2 is aged at room temperature, by the dipping Pt after ageing
Aluminium chloride in 80 DEG C of solvent evaporateds, then dry, roast, obtain the aluminium oxide of supporting Pt；The time of the ageing is 8h；Institute
The temperature for stating drying is 110 DEG C, and the time of drying is 10h；The atmosphere of the roasting is air atmosphere, and the temperature of roasting is 400
DEG C, the time of roasting is 4h；
Step 4: the aluminium oxide of supporting Pt described in step 3 is obtained dehydrogenation after pelletizing forms；It is described de-
Hydrogen catalyst is the macropore dehydrogenation that average pore size is 84nm, specific surface area 150m2/ g, pore volume 0.98mL/g.
Comparative example 2
The method for preparing dehydrogenation of this comparative example, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 90 DEG C, and the pretreated time is 1h；The temperature of the drying is 130 DEG C；The time of drying is
4h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: be 0.3% according to the mass percentage of Pt in dehydrogenation, it will be pretreated described in step 1
Aluminium oxide is added in the platinum acid chloride solution that mass concentration is 0.03g/mL, and it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 50 DEG C
After stirring dipping 8h, residul liquid-removing is removed, the aluminium chloride of dipping Pt is obtained；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 3: the aluminium chloride for impregnating Pt described in step 2 is aged under the conditions of 25 DEG C of room temperature, by the leaching after ageing
Then the aluminium chloride of stain Pt is dried in 80 DEG C of solvent evaporateds, roasting obtains the aluminium oxide of supporting Pt；The time of the ageing is
8h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The atmosphere of the roasting is air atmosphere, the temperature of roasting
It is 400 DEG C, the time of roasting is 4h；
Step 4: the aluminium oxide of supporting Pt described in step 3 is obtained dehydrogenation after pelletizing forms；It is described de-
Hydrogen catalyst is the macropore dehydrogenation that average pore size is 143nm, specific surface area 230m2/ g, pore volume 0.89mL/g.
Comparative example 3
The method for preparing dehydrogenation of this comparative example, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 90 DEG C, and the pretreated time is 1h；The temperature of the drying is 130 DEG C, and the time of drying is
4h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 4 times of the quality of pretreated aluminium oxide；
Step 3: be 0.3% according to the mass percentage of Pt in dehydrogenation, it will be modified oxidized described in step 2
Aluminium is added in the platinum acid chloride solution that mass concentration is 0.03g/mL, and it is 10 that lye, which is added dropwise, and adjusts pH, is stirred under the conditions of 50 DEG C
After impregnating 8h, residul liquid-removing is removed, obtains the modified chlorinated aluminium of dipping Pt；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, obtain the modified aluminas of supporting Pt；It is described
The time of ageing is 8h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The atmosphere of the roasting is air gas
Atmosphere, the temperature of roasting are 400 DEG C, and the time of roasting is 4h；
Step 5: the modified aluminas of supporting Pt described in step 4 is obtained dehydrogenation after pelletizing forms；Institute
Stating dehydrogenation is the macropore dehydrogenation that average pore size is 204nm, specific surface area 290m2/ g, pore volume are
1.24mL/g。
Comparative example 4
The method for preparing dehydrogenation of this comparative example, comprising the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains
To pretreated aluminium oxide；The mass concentration of the dust technology is 5%, and the quality of the dust technology is the 6 of the quality of aluminium oxide
Times；The pretreated temperature is 90 DEG C, and the pretreated time is 1h；The temperature of the drying is 130 DEG C, and the time of drying is
4h；The temperature of roasting is 400 DEG C, and the time of roasting is 5h；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, filled after 25 DEG C of room temperature stirrings
Divide drying, obtains modified aluminas；The mass concentration of modifying agent is 10% in the modifier solution, and the modifying agent is lemon
Sour sodium；The time of the stirring is 60min；The quality of the modifier solution is 4 times of the quality of pretreated aluminium oxide；
Step 3: being 0.3% according to the mass percentage of Pt in dehydrogenation, with platinum acid chloride solution in step 2
The modified aluminas is stirred dipping, obtains the modified chlorinated aluminium of dipping Pt；
The method of the stirring dipping are as follows: it is 0.03g/mL that modified aluminas described in step 2, which is added to mass concentration,
Platinum acid chloride solution in, be added dropwise lye adjust pH be 10, under the conditions of 50 DEG C stirring dipping 8h after, remove residul liquid-removing, obtain first
Modified aluminas after secondary stirring dipping；It is 0.03g/ that modified aluminas after first time stirring dipping, which is added to mass concentration,
In the platinum acid chloride solution of mL, it is 10 that lye, which is added dropwise, and adjusts pH, under the conditions of 50 DEG C after stirring dipping 8h, removes residul liquid-removing, is soaked
The modified chlorinated aluminium of stain Pt；Stirring for the first time impregnates platinum acid chloride solution used and second of stirring impregnates platinum acid chloride solution used
Volume ratio is 1:1；The lye is the ammonium hydroxide that mass concentration is 5%；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged under the conditions of 25 DEG C of room temperature, after ageing
Dipping Pt modified chlorinated aluminium in 80 DEG C of solvent evaporateds, then dry, roast, obtain the modified aluminas of supporting Pt；It is described
The time of ageing is 8h；The temperature of the drying is 110 DEG C, and the time of drying is 10h；The atmosphere of the roasting is air gas
Atmosphere, the temperature of roasting are 400 DEG C, and the time of roasting is 4h；
Step 5: the modified aluminas of supporting Pt described in step 4 is obtained dehydrogenation after pelletizing forms；Institute
Stating dehydrogenation is the macropore dehydrogenation that average pore size is 187nm, specific surface area 283m2/ g, pore volume are
1.45mL/g。
The dehydrogenation of above embodiments and comparative example is packed into fixed bed reactors and carries out dehydrogenating propane, is reacted
Condition are as follows: reaction temperature is 590 DEG C~600 DEG C, reaction pressure 0.1MPa, and propane air speed is 3.2h-1, reaction time 48h,
It obtains the performance test results and is shown in Table 1.Wherein conversion of propane, Propylene Selectivity and productivity of propylene are average value.
The reaction result of 1 dehydrogenation of table catalysis propane propylene
As can be seen from Table 1, in identical appraisement system, the dehydrogenation propane of 1~embodiment of embodiment 11
Conversion ratio be 36.1%~41.4%, corresponding Propylene Selectivity be 92.9%~98.1%, productivity of propylene be 34.1%~
40.5%, hence it is evident that be better than comparative example, show that dehydrogenation of the invention has superior reactivity in dehydrogenating propane reaction
Can, to the yield of propane activity of conversion with higher, higher Propylene Selectivity and target product.
Table 2 is the performance test results after the dehydrogenation of the embodiment of the present invention 6 regenerates 5 times, and dehydrogenation is again
Generation method is to restore in hydrogen atmosphere, the concrete operations of performance test after regenerating and regenerating are as follows: by the catalysis dehydrogenation after reaction
Agent is placed in pure hydrogen atmosphere, is 10 DEG C/min according to heating rate, is risen to 550 DEG C~610 DEG C from room temperature, to de- after reaction
Hydrogen catalyst is restored, and the recovery time is 2h~3h；Unstripped gas propane is passed through into the dehydrogenation after reduction to carry out instead
It answers, after raw material has reacted, switching hydrogen atmosphere is regenerated.Higher reaction is still presented after dehydrogenation regeneration of the invention
Performance shows that dehydrogenation of the invention has high anti-carbon, anti-sintering and inhibition halogen poisoning capability, and of the invention is de-
Hydrogen catalyst has high service life.
The performance test results after dehydrogenation regeneration 5 times of 2 embodiment of the present invention 6 of table
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, all according to invention skill
Art any simple modification substantially to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention
In the protection scope of scheme.
Claims (10)
1. a kind of dehydrogenation, which is characterized in that the dehydrogenation is using modified aluminas as carrier, using Pt as active group
Point, using perovskite containing Ga as auxiliary agent；The mass percentage of Pt is the quality of 0.1%~0.5%, Ga in the dehydrogenation
Percentage composition is 0.4%~3.1%.
2. a kind of dehydrogenation according to claim 1, which is characterized in that the molecular formula of the perovskite containing Ga is
LaxSr1-xCoyGa1-yO3, 0.1≤x≤0.9,0.1≤y≤0.9.
3. a kind of dehydrogenation according to claim 2, which is characterized in that the preparation method packet of the perovskite containing Ga
Include following steps:
Step 1: by dissolution of raw material in lye, continues plus lye to pH is 9.0~10.5, obtain the presoma of perovskite containing Ga；
The lye is the ammonium hydroxide that mass concentration is 10%~20%；The raw material is lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate；
Step 2: the presoma of perovskite containing Ga described in step 1 is obtained the titanium of calcium containing Ga successively by drying, roasting and grinding
Mine；The temperature of the drying is 90 DEG C~110 DEG C, and the time of drying is 10h~15h；The atmosphere of the roasting is air atmosphere,
The temperature of roasting is 800 DEG C~1000 DEG C, and the time of roasting is 5h~10h；The partial size of the perovskite containing Ga be 200 mesh~
300 mesh.
4. a kind of dehydrogenation according to claim 1, which is characterized in that the average pore size of the dehydrogenation is
95nm~325nm；The pore volume of the dehydrogenation is 1.2mL/g~1.7mL/g；The specific surface area of the dehydrogenation
For 260m2/ g~390m2/g。
5. a kind of dehydrogenation according to claim 1 or 2, which is characterized in that the matter of Ga in the dehydrogenation
Measuring percentage composition is 1.1%~3.1%.
6. a kind of method for preparing dehydrogenation as claimed in claim 1 or 2, which comprises the following steps:
It pre-processes, filters Step 1: aluminium oxide is placed in dust technology, the trapped substance being obtained by filtration is dried, roasting obtains pre-
The aluminium oxide of processing；
Step 2: pretreated aluminium oxide described in step 1 is placed in modifier solution, it is dry after being stirred at room temperature, changed
Property aluminium oxide；
Step 3: being stirred dipping to modified aluminas described in step 2 with platinum acid chloride solution, the modification of dipping Pt is obtained
Aluminium chloride；
Step 4: the modified chlorinated aluminium for impregnating Pt described in step 3 is aged at room temperature, by the dipping Pt after ageing
Modified chlorinated aluminium in 70 DEG C~80 DEG C solvent evaporateds, then dry, roast, grinding, obtain the modified aluminas of supporting Pt；
Step 5: perovskite containing Ga is uniformly mixed with the modified aluminas of supporting Pt described in step 4, obtained after forming
Dehydrogenation.
7. according to the method described in claim 6, it is characterized in that, the mass concentration of dust technology described in step 1 be 4%~
8%, the quality of dust technology is 4 times~8 times of the quality of aluminium oxide；Pretreated temperature described in step 1 is 80 DEG C~110
DEG C, the pretreated time is 0.5h~2h；The temperature of drying described in step 1 is 80 DEG C~150 DEG C, and the time of drying is 3h
~10h；The temperature of roasting described in step 1 is 300 DEG C~400 DEG C, and the time of roasting is 3h~6h；
The mass concentration of modifying agent is 5%~15% in modifier solution described in step 2, and the modifying agent is sodium carbonate, carbon
One or more of sour potassium, sodium acetate and sodium citrate；The quality of modifier solution described in step 2 is pretreated oxygen
3 times~6 times for changing the quality of aluminium；The time of stirring described in step 2 is 30min~90min.
8. according to the method described in claim 6, it is characterized in that, the method for stirring dipping described in step 3 are as follows: will be modified
Aluminium oxide is added in the platinum acid chloride solution that mass concentration is 0.01g/mL~0.03g/mL, and it is 9~11 that lye, which is added dropwise, and adjusts pH,
Under the conditions of 40 DEG C~70 DEG C after stirring dipping 5h~8h, residul liquid-removing is removed, obtains stirring the modified aluminas after dipping for the first time；
Modified aluminas after first time stirring dipping is added to the platinum acid chloride solution that mass concentration is 0.01g/mL~0.03g/mL
In, it is 9~11 that lye, which is added dropwise, and adjusts pH, under the conditions of 40 DEG C~70 DEG C after stirring dipping 5h~8h, removes residul liquid-removing, is impregnated
The modified chlorinated aluminium of Pt；The lye is the ammonium hydroxide that mass concentration is 5%~10%.
9. according to the method described in claim 6, it is characterized in that, the time of ageing described in step 4 is 5h~10h；Step
The temperature of drying described in four is 110 DEG C~130 DEG C, and the time of drying is 10h~15h；The atmosphere of roasting described in step 4
For air atmosphere, the temperature of roasting is 400 DEG C~600 DEG C, and the time of roasting is 4h~6h；Supporting Pt described in step 4 changes
Property aluminium oxide partial size be 200 mesh~300 mesh；Molding described in step 5 includes granulating and forming, pelletizing molding or integrally formed.
10. a kind of application of dehydrogenation as described in claim 1 in dehydrating alkanes alkene.
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