CN108295846A - A kind of alkane dehydrogenating catalyst and preparation method thereof - Google Patents
A kind of alkane dehydrogenating catalyst and preparation method thereof Download PDFInfo
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- CN108295846A CN108295846A CN201810141771.0A CN201810141771A CN108295846A CN 108295846 A CN108295846 A CN 108295846A CN 201810141771 A CN201810141771 A CN 201810141771A CN 108295846 A CN108295846 A CN 108295846A
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- dehydrogenating catalyst
- alkane dehydrogenating
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 238000002803 maceration Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002156 adsorbate Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000002860 competitive effect Effects 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 229910001648 diaspore Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- OKPZIQOBDZDBRW-UHFFFAOYSA-N [Pt].[K] Chemical group [Pt].[K] OKPZIQOBDZDBRW-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical group [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- -1 carrier Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- UUWDNZVBBUGKMK-UHFFFAOYSA-N dipotassium;dinitrate Chemical compound [K+].[K+].[O-][N+]([O-])=O.[O-][N+]([O-])=O UUWDNZVBBUGKMK-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of alkane dehydrogenating catalysts, including carrier, and Pt, the Sn and K element being supported on carrier, wherein the micropore accounting of 2 15nm of the carrier aperture is 5 30%, the micropore accounting of 15 85nm of aperture is 55 85%.It is carrier that the present invention, which has the aluminium oxide of specific pore size distribution, and this specific pore-size distribution is advantageous to the quick diffusion of reactant, reduces the time of contact of intermediate product and metal active position, hence it is evident that reduce the generation of carbon distribution.
Description
Technical field
The invention belongs to dehydrogenation fields, and in particular to a kind of alkane dehydrogenating catalyst and preparation method thereof.
Background technology
Propylene and isobutene are important industrial chemicals, and propylene is mainly used to produce polypropylene, acrylonitrile, acrylic acid, third
Olefine aldehydr etc. is the base stock of three big synthetic materials (plastics, rubber and fiber).Isobutene is used to production methyl tertbutyl
In addition ether, the tert-butyl alcohol, methyl methacrylate and butyl rubber etc. are also act as the alkylated raw material of low-carbon alkene.Effectively profit
Not only meet national low-carbon environment-friendly policy and circular economy concept with propane and iso-butane, but also there is good economic benefit and society to imitate
Benefit.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, carbon deposit and activity
The reason of metal sintering is always influence catalyst stability, therefore developing, there is the alkane dehydrogenating catalyst of high stability to become
The key of the technology.
Application No. is a kind of C16-C19 long-chain normal paraffins dehydrogenation of the invention of CN2008101178913 and its systems
Preparation Method and application disclose the large aperture strip aluminium oxide that its used carrier is diplopore distribution, which is suitable for long alkane
Hydrocarbon dehydrogenation, when being used for dehydrogenating low-carbon alkane, conversion ratio is relatively low.
5~150m of technology alumina support specific surface area that US4608360 patents provide2/ g, the hole of average pore size 30nm
It accounts for total pore volume ratio and is less than 18%, the hole of average pore size 60nm or more accounts for 55% or more total pore volume ratio, the catalyst
Major defect be for low carbon chain catalysis dehydrogenation reaction stability it is poor, and the service life is shorter.
Application No. is a kind of catalyst for dehydrogenation of saturated hydrocarbon of the invention of CN971044627 and preparation method thereof to disclose using double
The scheme of pore size distribution, wherein 5~100nm accounts for 20~35%, 100~1000nm accounts for 44~58%, which is suitable for long carbon
Paraffin dehydrogenation reacts, and when being used for dehydrogenating low-carbon alkane, conversion ratio is relatively low.
Invention content
The present invention in order to solve the problems existing in the prior art, provides a kind of alkane dehydrogenating catalyst and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is：
A kind of alkane dehydrogenating catalyst, including carrier, and Pt, Sn and K element for being supported on carrier, wherein the load
The micropore accounting of body aperture 2-15nm is 5-30%, the micropore accounting of aperture 15-85nm is 55-85%.Wherein, aperture 15-
85nm refers to being more than the micropore that 15nm is less than or equal to the apertures 85nm.
Further, the Pt elements carrying capacity is 0.1-0.4%, and platinum tin atom ratio is 1：0.5-1, platinum potassium atom ratio are 1：
0.2-1。
Further, the carrier is alumina support.
Further, the preparation method of the alumina support, including the following contents：
1) alumina precursor is dissolved in dilute hydrochloric acid, forms colloidal sol, reshaping；
2) products therefrom is dried at 120-150 DEG C after being molded, then roasts 3-8h at 800-1100 DEG C to get oxidation
Alumina supporter.
Further, the alumina precursor is boehmite, boehmite, gibbsite, diaspore, one
It is one or more in boehmite, gama-alumina, θ-aluminium oxide.
Further, the grain size of the alumina precursor is 70-120 μm.
The present invention also provides a kind of preparation methods of alkane dehydrogenating catalyst, including the following contents：
1) by Pt salt, Sn salt, K salt formation mixed solution soluble in water, the competition of mixed solution weight 2-8% is then added
Adsorbent obtains maceration extract；
2) alumina support is immersed in maceration extract, after having impregnated through drying, roast up to alkane dehydrogenating catalyst.
Further, in step 1), the competitive adsorbate is one in 2- acrylic acrylic acid, pyruvic acid, batanone acid
Kind is a variety of.
Further, in step 1), the competitive adsorbate dosage is the 2-8% of mixed solution quality.
Further, in step 2), alumina support is immersed in 1-5h in the maceration extract that temperature is 40~80 DEG C；Then
It is dried 1~4h at 80~120 DEG C, 4~8h is roasted at 400~600 DEG C to get alkane dehydrogenating catalyst.
Advantageous effect of the present invention：
One, the present invention is suitable for the catalyst that C3~C4 dehydrating alkanes produce monoolefine, which not only has preferably
Activity and selectivity, and there is higher stability, there is stronger anti-metal caking power and carbon accumulation resisting ability, thus can
With in the higher long period of operation of conversion per pass.
Two, the present invention uses the aluminium oxide with specific pore size distribution for carrier, and this specific pore-size distribution extremely has
Conducive to the quick diffusion of reactant, the time of contact of intermediate product and metal active position is reduced, hence it is evident that reduce the production of carbon distribution
It is raw.
Three, the present invention additionally uses competitive adsorbate in preparation process, is conducive to make Pt, Sn, K dispersion evenly, point
Cloth enhances the catalysis efficiency of catalyst on peculiar carrier, improves stability.
Specific implementation mode
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
It is prepared by carrier：By screen out 70~120 μm of boehmite original powder 50g and contain 5% dilute hydrochloric acid solution 62g,
It is uniformly mixed in tank at 70 DEG C, forms colloidal sol, be molded in oil ammonia column and obtain bead, dried at 120 DEG C, then exist
4h is roasted at 900 DEG C, is sieved after coolingBead to get carrier A1.
Catalyst preparation：A1 alumina carrier beads 20g obtained above is taken to be placed in infuser.Take platiniferous 0.01g/ml
Chloroplatinic acid aqueous solution 4ml, stanniferous 0.005g/ml stannous chloride aqueous solution 3.25ml, the 0.01g/ml containing potassium potassium nitrate it is molten
0.33g 2- acrylic acrylic acid is added in liquid 0.53ml, then adds deionized water 8.27g, is configured to maceration extract, is impregnated at 60 DEG C
Alumina support, dip time 2h.Then 2h is dried at 100 DEG C, is roasted 4h at 550 DEG C, is obtained catalyst A2
Embodiment 2
It is prepared by carrier：By screen out 70~120 μm of gamma-alumina original powder 38g and contain 5% dilute hydrochloric acid solution 50g,
It is uniformly mixed in tank at 60 DEG C, forms colloidal sol, be molded in oil ammonia column and obtain bead, dried at 140 DEG C, then 1000
6h is roasted at DEG C, is sieved after coolingBead to get carrier B 1.
Catalyst preparation：1 alumina globule 20g of carrier B obtained above is taken to be placed in infuser.Take platiniferous 0.01g/ml
Chloroplatinic acid aqueous solution 6ml, stanniferous 0.005g/ml stannous chloride aqueous solution 5.00ml, the 0.01g/ml containing potassium potassium nitrate it is molten
0.48g pyruvic acid is added in liquid 0.80ml, then adds deionized water 4.20g, is configured to maceration extract, is carried in 40 DEG C of oxide impregnation aluminium
Body, dip time 2h.Then 2h is dried at 80 DEG C, is roasted 6h at 600 DEG C, is obtained catalyst B2.
Embodiment 3
It is prepared by carrier：By screen out 70~120 μm of diaspore original powder 52g and contain 5% dilute hydrochloric acid solution 67g,
It is uniformly mixed in tank at 80 DEG C, forms colloidal sol, be molded in oil ammonia column and obtain bead, dried at 130 DEG C, then exist
5h is roasted at 1100 DEG C, is sieved after coolingBead to get support C 1.
Catalyst preparation：1 alumina globule 20g of support C obtained above is taken to be placed in infuser.Take platiniferous 0.01g/ml
Chloroplatinic acid aqueous solution 6ml, stanniferous 0.005g/ml stannous chloride aqueous solution 5.20ml, the 0.01g/ml containing potassium potassium nitrate it is molten
0.62g batanone acids are added in liquid 1.00ml, then add deionized water 4.79g, are configured to maceration extract, are carried in 50 DEG C of oxide impregnation aluminium
Body, dip time 3h.Then 3h is dried at 80 DEG C, is roasted 8h at 500 DEG C, is obtained catalyst C2.
Comparative example 1
It is prepared by carrier：According to CN201110324813.2, the boehmite for being 40 μm in 220.2g average particle sizes
The inorganic oxygen-containing chemical combination of boehmite original powder or other aluminium that 90g average grain diameters are 9~30 μm is separately added into original powder major ingredient
Then object is added 9g sesbania powders and adds extrusion after 130ml deionized waters are mediated fully, place 12h at room temperature, then protect with 90 DEG C
3h is held, carrier D1 is made in 750 DEG C of processing in the program drying of 120 DEG C of holding 10h.
Catalyst preparation：Using above-mentioned mixed oxidization alumina supporter D1, catalyst, catalyst are prepared according to 1 method of embodiment
D2。
Comparative example 2
It is prepared by carrier：It is 8 by weight ratio：1：1 aluminium hydroxide, boehmite and sesbania powder is uniformly mixed, and is added
15% nitric acid is extruded into strip after stirring with banded extruder, is then broken into 18~20 in 120 DEG C of dry 4h, 650 DEG C of roasting 8h
Mesh particle, the steam treatment 8h at 650 DEG C, obtains carrier E1.
Catalyst preparation：Using above-mentioned mixed oxidization alumina supporter E1, catalyst, catalyst are prepared according to 1 method of embodiment
E2。
Carrier aperture distribution is shown in Table 1.
1 carrier aperture of table is distributed
| 2~15nm (%) | 15~80nm (%) | |
| A1 | 28 | 55 |
| B1 | 15 | 72 |
| C1 | 7 | 80 |
| D1 | 53 | 42 |
| E1 | 40 | 15 |
Catalyst uses 500 DEG C of reduction activation 1h of hydrogen before dehydrogenation reaction, then in 610 DEG C of reaction temperature, propane quality
Air speed 3h-1, H2/C3H8Molar ratio is 2：Activity rating is carried out under conditions of 3,120h reaction results are shown in Table 2.
2 catalyst activity evaluation result of table
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or
It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection domain.
Claims (10)
1. a kind of alkane dehydrogenating catalyst, it is characterised in that：Including carrier, and Pt, Sn and K element for being supported on carrier,
The micropore accounting of the wherein described carrier aperture 2-15nm is 5-30%, the micropore accounting of aperture 15-85nm is 55-85%.
2. alkane dehydrogenating catalyst according to claim 1, it is characterised in that：The Pt elements carrying capacity is 0.1-0.4%, platinum
Tin atom ratio is 1：0.5-1, platinum potassium atom ratio are 1：0.2-1.
3. alkane dehydrogenating catalyst according to claim 1, it is characterised in that：The carrier is alumina support.
4. alkane dehydrogenating catalyst according to claim 3, it is characterised in that：The preparation method of the alumina support, packet
Include the following contents：
1) alumina precursor is dissolved in dilute hydrochloric acid, forms colloidal sol, reshaping；
2) products therefrom is dried at 120-150 DEG C after being molded, then roasts 3-8h at 800-1100 DEG C to get carrying alumina
Body.
5. alkane dehydrogenating catalyst according to claim 4, it is characterised in that：The alumina precursor is to intend thin water aluminium
It is one or more in stone, boehmite, gibbsite, diaspore, boehmite, gama-alumina, θ-aluminium oxide.
6. alkane dehydrogenating catalyst according to claim 4, it is characterised in that：The grain size of the alumina precursor is 70-
120μm。
7. the preparation method of alkane dehydrogenating catalyst as described in claim 1-6 is any, which is characterized in that including the following contents：
1) by Pt salt, Sn salt, K salt formation mixed solution soluble in water, competitive adsorbate is then added and obtains maceration extract；
2) alumina support is immersed in maceration extract, after having impregnated through drying, roast up to alkane dehydrogenating catalyst.
8. the preparation method of alkane dehydrogenating catalyst according to claim 7, it is characterised in that：In step 1), the competition
Adsorbent is one or more in 2- acrylic acrylic acid, pyruvic acid, batanone acid.
9. the preparation method of alkane dehydrogenating catalyst according to claim 7, it is characterised in that：In step 1), the competition
Adsorbent amount is the 2-8% of mixed solution quality.
10. the preparation method of alkane dehydrogenating catalyst according to claim 7, it is characterised in that：In step 2), by aluminium oxide
Carrier impregnation 1-5h in the maceration extract that temperature is 40~80 DEG C；Then 1~4h is dried at 80~120 DEG C, 400~
4~8h is roasted at 600 DEG C to get alkane dehydrogenating catalyst.
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| CN113171801A (en) * | 2020-11-30 | 2021-07-27 | 谷育英 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof |
| CN113694923A (en) * | 2021-09-29 | 2021-11-26 | 淄博市翔力致高新材料有限责任公司 | Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof |
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