CN110560039B - Propane dehydrogenation catalyst and preparation method thereof - Google Patents
Propane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN110560039B CN110560039B CN201810566736.3A CN201810566736A CN110560039B CN 110560039 B CN110560039 B CN 110560039B CN 201810566736 A CN201810566736 A CN 201810566736A CN 110560039 B CN110560039 B CN 110560039B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000001294 propane Substances 0.000 title claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 39
- 238000002791 soaking Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 76
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 60
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 44
- 238000011156 evaluation Methods 0.000 description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 37
- 229910021641 deionized water Inorganic materials 0.000 description 37
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 28
- 239000011651 chromium Substances 0.000 description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- PXXRROSTRSLPET-UHFFFAOYSA-J C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] PXXRROSTRSLPET-UHFFFAOYSA-J 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical group [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- 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
- C07C5/3335—Catalytic processes with metals
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a propane dehydrogenation catalyst and a preparation method thereof, and mainly solves the problem that the Cr-series dehydrogenation catalyst prepared by the prior art is low in activity. The dehydrogenation catalyst adopted by the invention comprises the following components in parts by weight: a) 1-30 parts of Cr and/or W element or oxide thereof; b) 0.01-5 parts of at least one element selected from IVB group of the periodic table or its oxide; c) 69-96 parts of alumina carrier, the problem is solved well, and the method can be used for industrial application of propane dehydrogenation.
Description
Technical Field
The invention relates to a propane dehydrogenation catalyst and a preparation method thereof.
Background
The catalytic dehydrogenation process is a commonly used preparation method for low-carbon olefins at present, and generally, low-carbon alkanes are subjected to dehydrogenation to prepare corresponding olefins, wherein propylene is obtained by dehydrogenation of corresponding propane. The propylene has wide application, and is used for producing acrylonitrile, propylene oxide, acrylic acid, isopropanol and the like besides the polypropylene. However, the increase of the demand of polypropylene is always the key of the increase of the demand of propylene, the annual growth rate of propylene is expected to be kept at 5% in the future, and in order to enable the yield of propylene to meet the demand of downstream derivatives, the method for preparing propylene by adopting ethylene co-production and light oil (naphtha and light diesel oil) cracking process is a method which cannot meet the increase of the demand, so that the method for preparing propylene by dehydrogenation reaction by using propane as a raw material is vigorously developed in various countries in the world. The propane dehydrogenation reaction is a strong endothermic reaction and is limited by thermodynamic equilibrium, so that a relatively ideal propylene yield can be obtained under the conditions of low pressure and high temperature, and the problems of poor catalyst performance, low selectivity and the like caused by the aggravation of propane cracking reaction and deep dehydrogenation due to excessively high reaction temperature.
The industrial propane dehydrogenation technology mainly comprises a Pt catalyst and a Cr catalyst, and comprises an Oleflex process of UOP, a Catofin process of Lummus, a STAR process of Uhde, a PDH process of Linde, an FBD process developed by Snamprogetti-Yarsintez cooperation and the like, wherein the industrial devices are mostly the Oleflex technology and the Catofin technology, and the catalysts applied to the Oleflex technology and the Catofin technology are respectively the Pt catalyst and the Cr catalyst. The Pt dehydrogenation catalyst is used for dehydrogenation of low-carbon alkane, has the advantages of environmental friendliness, high activity and the like, and has high price, complex preparation and high requirement on purity of reaction raw materials. The Cr catalyst has low price, relatively high activity and low requirement on the purity of raw materials, but has certain influence on the environment, frequent regeneration is needed in the reaction process, the regeneration and other conditions are harsh, and the performance requirements on all aspects of the Cr catalyst are higher.
Chinese patent CN103769156 uses ammonia treated alumina as carrier, Cr as active component, potassium, manganese, cobalt, iron, nickel and the like as auxiliary agent, and prepares dehydrogenation catalyst by co-impregnation method, the Cr content is 2-6%, the auxiliary agent content is 0.1-5%, the catalyst has better selectivity, but the activity is relatively low. The dehydrogenation catalyst disclosed in the Chinese patent CN100406415C has a chromium oxide content of 5-30%, and the actual chromium oxide content in example 1 is about 24%, which belongs to a high Cr content catalyst. Chinese patent CN 102019178A reports a catalyst for preparing propylene by propane dehydrogenation, and preparation and application thereof, wherein the content of chromium oxide is 10-20%, the reaction temperature is 590 ℃, the absolute pressure is 0.105MPa, and the space velocity is 900 hours-1Under the condition, the conversion rate of propane is 40% and the selectivity of propylene is 85% when the reaction is carried out for 5 min. Chinese patent CN101940922B reports a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein chromium is used as an active metal component, chromium-containing alumina is used as a carrier, the weight content of chromium oxide in the carrier is 2.0-15.0%, and the activity of the catalyst is improved. Chinese patent CN101940922A reports a low-carbon alkane dehydrogenation catalyst, which takes Cr as an active component and alkali metal as an auxiliary agent at a reaction temperatureThe temperature is 645 ℃ and the liquid hourly space velocity is 600 hours-1The conversion of propane at normal pressure for 30 minutes of the reaction was 47%, and the selectivity to propylene was about 89%. Although the catalyst has better activity, the content of the chromium oxide is up to 10-45% by weight of the catalyst, which undoubtedly puts higher requirements on environmental protection. According to the laboratory verification of the inventor, the catalyst is easy to deposit carbon and has low stability.
Although the propane dehydrogenation catalyst has been developed, the catalyst still has problems of low activity, especially the selectivity and stability of the existing Cr-based dehydrogenation catalyst are also insufficient. W has more applications in the petrochemical industry, and can enable the catalyst to have better catalytic activity and selectivity through the synergistic effect with Cr. According to the invention, Cr and/or W are used as the active components of the catalyst, and the IVB group of the periodic table of elements is added in the preparation process, and the result shows that the propane dehydrogenation catalyst prepared by the method has high catalyst activity and good industrial application prospect.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low activity of the propane dehydrogenation catalyst in the prior art, and provides a propane dehydrogenation catalyst. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem. The third technical problem to be solved by the present invention is to provide a catalyst for propane dehydrogenation corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the propane dehydrogenation catalyst comprises the following components in parts by weight:
a) 1-30 parts of Cr and/or W element or oxide thereof;
b) 0.01-5 parts of at least one element selected from IVB group of the periodic table or its oxide;
c) 69-96 parts of Al2O3And (3) a carrier.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 5-23 parts by weight of the propane catalyst.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 10-18 parts by weight of the propane catalyst.
In the above technical solution, more preferably, the element is selected from Cr and W or an oxide thereof, wherein the weight ratio of Cr to W is: (0.1-10): 1. in this case, the use of both Cr and W has an unexpected synergistic effect in improving the catalytic activity of the propane dehydrogenation catalyst.
In the above technical solution, preferably, the alloy simultaneously includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W elements is: (0.25-5): 1.
in the technical scheme, the part of the element selected from IVB group of the periodic table or the oxide thereof is 0.01-3 parts by weight of the propane catalyst, wherein the element of IVB group is selected from at least one of Ti and Zr.
In the technical scheme, the range of the IVB group element or the oxide thereof in the periodic table is 0.3-3 parts by weight of the propane catalyst.
In the above technical solution, more preferably, the group ivb element of the periodic table or an oxide thereof is a mixture of Ti and Zr, where Ti: the weight ratio of Zr is (0.25-5): 1, and the mixture of Ti and Zr has unexpected synergistic effect on the aspect of improving the catalyst activity of the propane dehydrogenation catalyst.
The Cr element and the W element are used together and cooperate with the IVB element, so that the catalyst has unexpected synergistic effect on the aspect of improving the catalyst activity of the propane dehydrogenation catalyst.
In the technical scheme, the specific surface of the adopted alumina carrier is 50-500 m2(g) the pore diameter is 5-40 nm.
In the technical scheme, more preferably, the specific surface range of the alumina carrier is 117-350 m2The pore diameter is 8-25 nm.
To solve the second technical problem, the invention adopts the following technical scheme: a catalyst for propane dehydrogenation and a preparation method thereof comprise the following steps:
a) pressing and screening the alumina with certain specific surface area and aperture, selecting 20-40 meshes for screening, and roasting at 400-600 ℃ for 0.5-12 hours to obtain a pretreated carrier I;
b) mixing a carrier I with a soluble salt solution containing Cr and/or W and a soluble solution in the IVB group of the periodic table to obtain a mixture I, and adjusting the pH value of the mixture I to 1-7 by using an inorganic ammonia or inorganic ammonium salt solution at the temperature of 10-80 ℃ to obtain a mixture II;
c) and (3) soaking the mixture II for 0.5-8 hours at the temperature of 10-100 ℃, filtering, drying, and roasting at 300-800 ℃ for 0.5-12 hours to obtain the required propane dehydrogenation catalyst.
The soluble salt of Cr can be selected from one of nitrate, acetate or oxalate; the W soluble salt is selected from tungstate, metatungstate or acetate. Ti and Zr are selected from one of nitrate, acetate and other soluble salts.
In the technical scheme, the preferable scheme of the inorganic ammonia or inorganic ammonium salt is selected from ammonia water, ammonium carbonate or ammonium bicarbonate, and the preferable range of the pH value of the solution is 1-7, and the more preferable range is 1-3; the preferable range of the dipping temperature is 50-80 ℃, the preferable range of the dipping time is 1-3 hours, the preferable range of the roasting temperature of the catalyst is 400-600 ℃, and the preferable range of the roasting time is 4-8 hours.
The third technical problem to be solved by the invention is that the technical scheme adopted by the invention is as follows: the reaction raw material is propane, and the reaction conditions are as follows: the reaction pressure is 0.01-1 MPa, the temperature is 520-650 ℃, and the mass space velocity is 0.2-8 h-1(ii) a The reaction raw material and the catalyst are contacted and reacted to obtain the propylene. The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed reactor, and the process for preparing propylene by propane dehydrogenation comprises the following steps:
the flow rate of propane gas is adjusted through a mass flow meter, the propane gas enters a preheating zone to be preheated, then the propane gas enters a reaction zone, a heating section and a reaction section of a reactor are heated by electric heating wires to reach a preset temperature, and the length of a reaction tube of the reactor is about 400-580 mm, wherein the inner diameter of the reaction tube is phi 9 mm-phi 6 mm. The reacted gas was passed through a condensing pot and then analyzed for composition by gas chromatography.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: loading about 0.5 g of catalyst into isothermal reactor with internal diameter of phi 9 mm-phi 6mm, reaction pressure being normal pressure and gas mass space velocity of 1.0 hr-1And the reaction temperature is 580 ℃. The conversion rate of the propane is obtained by multiplying the content of the propane which accounts for the sum of the contents of all gas-phase products after the reaction by 100 percent; selectivity of olefin as a percentage of propylene content in other gas components than propane after reaction, i.e. propylene content divided by C1、C2、C4And the percentage of the sum of the propylene contents.
When alumina is used as a carrier, the Cr-based catalyst commonly used for propane dehydrogenation has strong surface acidity, so that the catalyst is easy to deposit carbon to cause the reduction of the activity of the catalyst. The W element as VIB group has several variable valence states, and Cr and/or W together can effectively change the acid-base distribution and surface property of catalyst surface by adding IVB element, so that the catalyst has high activity. When the catalyst obtained by adopting the preparation conditions is used for propane dehydrogenation reaction, the catalyst has the advantages of 43% propane conversion rate and 90.9% propylene selectivity, and achieves better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
52.66 g of chromium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 15nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst.
The flow rate of propane gas is regulated by a mass flow meter, the propane gas enters a preheating zone for preheating, and then enters a reaction zone, a heating section and a reaction section of a reactor are heated by electric heating wires to reach a preset temperature, and the reactor is a quartz tube with the inner diameter of phi 9 mm-phi 6mm and the length of 400 mm. The reacted gas was passed through a condensing pot and then analyzed for composition by gas chromatography.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: 0.5 g of the catalyst is loaded into the isothermal fixed bed reactor, the reaction pressure is normal pressure, and the gas mass space velocity is 1.0 hour-1And the reaction temperature is 580 ℃. The results are shown in Table 1.
[ example 2 ]
52.66 g of chromium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 87 g of a solution having a specific surface area of 340m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 9nm, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 3 ]
52.66 g of chromium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 87 g of a specific surface area 173m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 12nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 4 ]
52.66 g of chromium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 87 g of a solution having a specific surface area of 45m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the aperture of 28nm per gram, then soaking the alumina carrier in a water bath with the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven with the temperature of 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast the sample for 4 hours at the temperature of 550 ℃ to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 5 ]
Weigh 52.66 grams of nitric acidChromium, 10.44 g zirconium nitrate, was added to 100 ml deionized water, followed by 87 g specific surface area 117m2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 6 ]
Ammonium tungstate 10.94 g and sodium titanate 3.78 g were weighed into 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 7 ]
Ammonium tungstate 10.94 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 8 ]
52.66 g of chromium nitrate, 1.89 g of sodium titanate and 5.22 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 9 ]
52.66 g of chromium nitrate, 1.26 g of sodium titanate and 6.96 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 7 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 10 ]
31.44 g of chromium oxalate, 7.40 g of titanium nitrate and 3.48 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 5 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The prepared catalyst was charged into a fixed bed reactor, and activity evaluation was performed at 550 ℃ and the results are shown in table 1.
[ example 11 ]
Ammonium tungstate 10.94 g, sodium titanate 1.89 g and zirconium nitrate 5.22 g were weighed into 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 7 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 12 ]
Ammonium tungstate 10.94 g, sodium titanate 1.26 g and zirconium acetate 5.32 g were weighed into 100 ml of deionized water, and 87 g of specific surface area 117m was added2The alumina carrier with the aperture of 15nm is used for regulating the pH value of the solution to 3 by using 2.5 percent ammonia water, and then the solution is soaked in a water bath at the temperature of 80 ℃ for 1 hour, and a sample is taken out to be put inFiltering, drying in a 120 ℃ oven for 8 hours, and then putting the sample into a muffle furnace to be roasted for 4 hours at 550 ℃ to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 13 ]
Ammonium tungstate 10.94 g, sodium titanate 2.52 g and zirconium acetate 2.66 g were weighed into 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 14 ]
26.33 g of chromium nitrate, 2.59 g of tungsten acetate and 3.78 g of sodium titanate were weighed into 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 15 ]
13.17 g of chromium nitrate, 2.73 g of ammonium tungstate and 3.78 g of sodium titanate were weighed into 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 16 ]
60.57 g of chromium nitrate, 12.54 g of ammonium tungstate and 3.78 g of sodium titanate were weighed into 100 ml of deionized water, and 87 g of specific surface area 117 was addedm2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 17 ]
39.5 g of chromium nitrate, 8.18 g of ammonium tungstate and 3.78 g of sodium titanate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 18 ]
47.4 g of chromium nitrate, 9.81 g of ammonium tungstate and 3.78 g of sodium titanate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 19 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate and 10.44 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 20 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 1.89 g of sodium titanate and 5.22 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 21 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 1.89 g of sodium titanate and 5.22 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 22 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 1.89 g of sodium titanate and 5.22 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 23 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 1.26 g of sodium titanate and 6.96 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The alumina carrier with the pore diameter of 15nm is used for regulating the pH value of the solution to 3.5 by using 2.5 percent ammonia water, then the solution is soaked in a water bath at the temperature of 50 ℃ for 1 hour, a sample is taken out for filtration, and the sample is dried in a baking oven at the temperature of 120 DEG CAnd drying for 8 hours, and then putting the sample into a muffle furnace to be roasted for 4 hours at the temperature of 550 ℃ to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 24 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 1.26 g of sodium titanate and 6.96 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 25 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 1.26 g of sodium titanate and 6.96 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 26 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.52 g of sodium titanate and 3.48 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 27 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 2.52 g of sodium titanate, and 3.48 g of zirconium nitrate were weighed and added to 100 ml of a solutionAdding 87 g of specific surface area 117m into the ionized water2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 28 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 2.52 g of sodium titanate and 3.48 g of zirconium nitrate were weighed and added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 29 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 0.53 g of sodium titanate and 8.7 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 30 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 0.53 g of sodium titanate and 8.7 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. Examination and evaluation condition of the same entityExample 1, the results are shown in Table 1.
[ example 31 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 0.53 g of sodium titanate and 8.7 g of zirconium nitrate were weighed and added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 32 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 3.15 g of sodium titanate and 1.74 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 33 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 3.15 g of sodium titanate and 1.74 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 34 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 3.15 g of sodium titanate and 1.74 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The pH value of the solution is adjusted by 2.5 percent ammonia water on an alumina carrier with the aperture of 15nmAnd 3.5, soaking in a water bath at 50 ℃ for 1 hour, taking out the sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 1
42.13 g of chromium nitrate and 2.19 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 2
10.94 g of ammonium tungstate was weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 3
52.66 g of chromium nitrate, 0.68 g of sodium carbonate and 3.03 g of ferric nitrate were weighed into 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 4
10.53 g of chromium nitrate and 8.75 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 87 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The evaluation conditions were the same as in example 1, and the results are shown in Table 1.
TABLE 1
Claims (9)
1. The propane dehydrogenation catalyst comprises the following components in parts by weight:
a) 1-30 parts of oxides of two elements of Cr and W;
b) 0.01-5 parts of a mixture of oxides of two elements of Ti and Zr in the IVB group of the periodic table;
c) 69-96 parts of Al2O3And (3) a carrier.
2. The propane dehydrogenation catalyst according to claim 1, wherein the amount of the oxide of each of the elements Cr and W is 5 to 23 parts by weight based on the weight of the propane dehydrogenation catalyst.
3. The propane dehydrogenation catalyst of claim 2, wherein the weight ratio of Cr to W elements in the catalyst is: (0.1-10): 1.
4. the propane dehydrogenation catalyst according to claim 1, wherein the amount of the mixture of oxides of two elements, Ti and Zr, in group IVB of the periodic Table is 0.01 to 3 parts by weight based on the weight of the propane dehydrogenation catalyst.
5. The propane dehydrogenation catalyst according to claim 4, wherein the amount of the mixture of oxides of two elements of Ti and Zr in group IVB of the periodic Table is 0.3 to 3 parts.
6. The propane dehydrogenation catalyst of claim 4, wherein the molar ratio of Ti: the weight ratio of Zr is (0.25-5): 1.
7. The propane dehydrogenation catalyst of claim 1, characterized by Al2O3The specific surface area of the carrier is 50-500 m2The pore diameter is 5-40 nm.
8. The propane dehydrogenation catalyst of claim 7, characterized by Al2O3The specific surface area of the carrier is 117-350 m2The pore diameter is 8-25 nm.
9. A method of preparing a catalyst for propane dehydrogenation as claimed in any of claims 1 to 8 comprising the steps of:
a) al with a certain specific surface area and aperture2O3Tabletting and screening the carrier, selecting 20-40 meshes for screening, and roasting at 400-600 ℃ for 0.5-12 hours to obtain a pretreated carrier I;
b) mixing a carrier I with a required amount of soluble solution containing Cr and W and soluble solution in IVB group of the periodic table of elements to obtain a mixture I, and adjusting the pH value of the mixture I to 1-7 by using inorganic ammonia or inorganic ammonium salt solution at the temperature of 10-80 ℃ to obtain a mixture II;
c) and (3) soaking the mixture II for 0.5-8 hours at the temperature of 10-100 ℃, filtering, drying, and roasting at 300-800 ℃ for 0.5-12 hours to obtain the required propane dehydrogenation catalyst.
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