CN110560037B - Method for preparing propylene by propane dehydrogenation - Google Patents
Method for preparing propylene by propane dehydrogenation Download PDFInfo
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- CN110560037B CN110560037B CN201810566721.7A CN201810566721A CN110560037B CN 110560037 B CN110560037 B CN 110560037B CN 201810566721 A CN201810566721 A CN 201810566721A CN 110560037 B CN110560037 B CN 110560037B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000001294 propane Substances 0.000 title claims abstract description 107
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 153
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 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 60
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 51
- 239000011148 porous material Substances 0.000 claims description 50
- 238000001914 filtration Methods 0.000 claims description 49
- 238000002791 soaking Methods 0.000 claims description 49
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 104
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 82
- 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 74
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 50
- 235000011114 ammonium hydroxide Nutrition 0.000 description 50
- 239000008367 deionised water Substances 0.000 description 49
- 229910021641 deionized water Inorganic materials 0.000 description 49
- 238000002360 preparation method Methods 0.000 description 42
- 235000010333 potassium nitrate Nutrition 0.000 description 41
- 239000004323 potassium nitrate Substances 0.000 description 41
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 35
- 239000007858 starting material Substances 0.000 description 35
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 30
- 239000011651 chromium Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 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 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004817 gas chromatography 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 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
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical group [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/647—
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for preparing propylene by propane dehydrogenation, which mainly solves the problem of low selectivity of Cr-series dehydrogenation catalysts prepared by the prior art. The method adopts the direct contact reaction of a propane raw material and a catalyst to obtain the propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 510-660 ℃, and the mass space velocity is 0.1-9 h‑1(ii) a The catalyst comprises the following components in parts by weight: a) 2-30 parts of Cr and/or W element or oxide thereof; b) 0-5 parts of alkali metal element or oxide thereof; c)0 to 5 parts of at least one element selected from group VB of the periodic table or an oxide thereof; d) 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 method for preparing propylene by propane dehydrogenation.
Background
Propylene is generally obtained as a byproduct in oil refineries and chemical plants, and although MGG, catalytic cracking process for producing propylene in high yield is developed and popularized, the propylene byproduct from oil refineries and chemical plants still cannot meet the market demand, and especially, the demand for propylene will increase at a rate of 5% in the future with the increase of the consumption of downstream derivatives such as polypropylene, acrylonitrile, propylene oxide and the like. In the new method for increasing the yield of the propylene, the raw material propane is directly dehydrogenated to prepare the propylene, and the product is single, and the process is relatively simple, so that the method is favored by people. Industrial dehydrogenation processes in the world include Oleflex process by UOP, Catofin process by rumis, STAR process by philips oil, and Snamprogetti fluidized bed dehydrogenation process developed by russian russell research institute in conjunction with Snamprogetti engineering, italy, and the like. The Oleflex process adopts a moving bed continuous regeneration type reaction system; the Catofin and STAR process adopts a fixed bed intermittent regeneration reaction system; and the Snamprogetti process adopts a fluidized bed reaction regeneration system. In addition, there are alkane dehydrogenation technologies developed in conjunction with Linde and BASF.
The catalyst systems adopted by the propane dehydrogenation technology are a Pt-based catalyst and a Cr-based catalyst, wherein the industrial devices are mostly an Oleflex technology and a Catofin technology, and the catalysts used by the Oleflex technology and the Catofin technology are respectively the Pt-based catalyst and the Cr-based catalyst. The Pt dehydrogenation catalyst is used for dehydrogenation of low-carbon alkane, has the advantages of environmental friendliness, high activity and the like, but has high price, complex preparation and high requirement on purity of reaction raw materials. The Cr series catalyst has low price, relatively high activity, low requirement on the purity of raw materials, certain influence on the environment, frequent regeneration in the reaction process, harsh dehydrogenation conditions and the like. The Catofin process converts propane to propylene over a catalyst bed in a reaction section. The fresh propane feed is combined with propane recycle from the bottoms of the product separation column and the de-oiling column overhead as feed to the reactor. The raw material is heated and gasified by steam and a heat exchanger, and the gasified material and the discharged material of the reactor are heated again after heat exchange in the heat exchanger for discharging the raw material in a row. The heated gasification mass is heated in a feed heating furnace to a reaction temperature and then fed to a reactor. The hot discharge material of the reactor is cooled after heat exchange with the raw material of the reactor, and is sent to the compression section of the device. The hydrocarbon was maintained at 0.05MPa abs in the reactor. While the system is still under vacuum, the reactor is thoroughly purged with steam, thereby sweeping the catalyst and residual hydrocarbons from the reactor and into a recovery section.
Chinese patent CN 105727930 reports a catalyst for preparing propylene by direct dehydrogenation of propane, which takes regular mesoporous alumina-zirconia or alumina-ceria composite oxide as a carrier, chromium oxide as an active component and an alkali metal additive, and the catalyst has higher propane conversion rate and propylene selectivity. 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 CN101940922A reports a low-carbon alkane dehydrogenation catalyst, which takes Cr as an active component and alkali metal as an auxiliary agentThe reaction 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 method for preparing propylene by propane dehydrogenation has been greatly developed, the problems of low catalyst selectivity and the like still exist, and particularly, the conventional Cr-based dehydrogenation catalyst has the activity of improving by using an alkali metal element or a transition metal element as an auxiliary agent, but is still insufficient in the aspects of selectivity, stability and the like. W has more applications in the petrochemical industry, and the synergistic effect of W and Cr can make the catalyst have better catalytic selectivity and activity. The invention uses Cr and/or W as the active component of the catalyst, and the elements of the IA and VB groups in the periodic table of elements are added in the preparation process, thereby better solving the problem of lower selectivity of the catalyst and having good application prospect.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low selectivity of the propane dehydrogenation catalyst in the prior art, and provides a method for preparing propylene by propane dehydrogenation. 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.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a method for preparing propylene by propane dehydrogenation comprises the step of directly contacting and reacting a propane raw material with a catalyst to obtain propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 510-660 ℃, and the mass space velocity is 0.1-9 h-1(ii) a The catalyst comprises the following components in parts by weight:
a) 2-30 parts of Cr and/or W element or oxide thereof;
b)0 to 5 parts of at least one element of group IA or an oxide thereof;
c)0 to 5 parts of at least one element selected from group VB of the periodic table or an oxide thereof;
d) 69-96 parts of Al2O3And (3) a carrier.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 5-20 parts by weight of the propane catalyst.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 10-20 parts by weight of the propane catalyst.
In the above technical solution, it is more preferable that the alloy further includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W elements is: (0.1-9): 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 comprises Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W elements is: (0.25-4): 1.
in the technical scheme, the part of the elements selected from IA group of the periodic table or the oxides thereof is 0.01-3 parts by weight of the propane catalyst, wherein the elements of IA group are selected from at least one of Li, Na, K, Rb and Cs.
In the technical scheme, the part of the element selected from the VB group in the periodic table or the oxide thereof is 0.01-3 parts by weight based on the weight part of the propane catalyst, wherein the element selected from the VB group is at least one of V, Nb and Ta.
In the above technical solution, it is more preferable that the group vb element of the periodic table or the oxide thereof is a mixture of V and Nb.
In the above technical solution, more preferably, the group vb element of the periodic table or an oxide thereof is a mixture of V and Ta.
In the above technical solution, the preferable range of the part of the vb group element or the oxide thereof in the periodic table is 0.2 to 3 parts by weight of the propane catalyst.
In the above embodiments, the group vb element or its oxide is a mixture of V, Nb and Ta, which is the most preferable embodiment. In this case, the combination of group vb element or its oxide V, Nb and Ta in the catalyst has an unexpected synergistic effect in improving the catalyst activity of the propane dehydrogenation catalyst.
In the technical scheme, the VB group element or the VB group element oxide and the IA group element or the VA group element oxide are used together, so that the unexpected synergistic effect on the aspect of improving the catalyst activity of the propane dehydrogenation catalyst is achieved.
The Cr element and the W element are used together and cooperate with the VB 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 above technical solution, it is more preferable that the specific surface area of the alumina carrier is 117 to 350m2The pore diameter is 8-25 nm.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a propane dehydrogenation catalyst comprising the steps of:
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 soluble solutions in the IA group and the VB group of the periodic table of elements in required amounts 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. Li, Na, K, Rb and Cs are selected from one of nitrate, carbonate or acetate and other soluble salts; v, Nb and Ta are selected from one of their 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 method for producing propylene of the invention focuses on the reaction section, and propane is converted into propylene through the catalyst bed. The fresh propane feed is combined with a propane recycle from the bottom of the product separation column as feed to the reactor. The raw material is heated and gasified by steam and a heat exchanger, and the heated and gasified material is heated to the reaction temperature in a feeding heating furnace and then sent to a reactor. The hot discharge material of the reactor is cooled after heat exchange with the raw material of the reactor, and is sent to the compression section of the device. The hydrocarbon is maintained at a certain negative pressure in the reactor, while the system is still under vacuum conditions, the reactor is thoroughly purged with steam, thereby sweeping the catalyst and residual hydrocarbon from the reactor and entering the recovery section. The regeneration air is provided by a regeneration air turbine or air compressor which is preheated early in the air heater before entering the reactor. The regeneration air, in addition to serving to burn the catalyst to remove coke, is also used to restore the bed temperature to the initial operating conditions. During regeneration, heat is supplemented by controlled injection of fuel gas, which is combusted within the catalyst bed. When the regeneration is completed, the reactor is pumped to vacuum again, and the next operation cycle is entered.
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 quartz tube of which the inner diameter is phi 9 mm-phi 6mm is about 400-580 mm. The reacted gas was passed through a condensing pot and then analyzed for composition by gas chromatography. 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 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 propylene containsPercentage of the sum of the amounts.
In the process of preparing propylene by propane dehydrogenation, Cr and/or W are used as main active components, and elements in the IA group and the VB group of the periodic table of elements are added simultaneously, so that the acid-base distribution, the surface characteristics and the like of the surface of the catalyst can be effectively changed, and the catalyst has higher selectivity and activity. The catalyst obtained by adopting the preparation conditions is used for the reaction of preparing propylene by propane dehydrogenation, the conversion rate of propane is 45 percent, the selectivity of propylene is 91.5 percent, and better technical effects are obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed into 100 ml of deionized water, and 81 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 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 the 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 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 a reaction temperature of 580 ℃. The results are shown in Table 1.
[ example 2 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate are weighed into 100 ml of deionized water, and 81 g of chromium nitrate, potassium nitrate and ammonium vanadate each having a specific surface area of 340m are added2Alumina carrier with 9nm pore diameter, 2.5% ammonia water to regulate pH value of the solution3.5, soaking in a water bath at 80 ℃ 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 3 ] A method for producing a polycarbonate
79 g of chromium nitrate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed into 100 ml of deionized water, and 81 g of a specific surface area of 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 4 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate are weighed into 100 ml of deionized water, and 81 g of a solution having a specific surface area of 45m is 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 5 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate and 12.14 g of niobium oxalate were weighed and added to 100 ml of deionized water, and 81 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. Propane feedstockThe reaction was carried out under the same reaction conditions as in example 1 with the above-mentioned catalyst, and the results are shown in Table 1.
[ example 6 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate and 3.42 g of sodium tantalate are weighed into 100 ml of deionized water, and 81 g of water having a specific surface area of 117m is 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 7 ]
16.4 g of ammonium tungstate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed, and the weighed materials were added to 100 ml of deionized water, followed by addition of 81 g of a specific surface area of 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 8 ]
16.4 g of ammonium tungstate, 2.15 g of potassium nitrate and 12.14 g of niobium oxalate were weighed and added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 9 ]
16.4 grams of ammonium tungstate was weighed,2.15 g potassium nitrate and 3.42 g sodium tantalate are added into 100 ml deionized water, and then 81 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 reaction conditions were the same as in example 1, and the results are shown in Table 1.
[ example 10 ]
16.4 g of ammonium tungstate, 4.16 g of lithium nitrate and 3.42 g of sodium tantalate are weighed and added to 100 ml of deionized water, and 81 g of 173m in specific surface area are added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with the aperture of 13nm to 3.5 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 11 ]
16.4 g of ammonium tungstate, 2.74 g of sodium nitrate and 3.42 g of sodium tantalate are weighed into 100 ml of deionized water, and 81 g of a specific surface area of 117m is 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 reaction conditions were the same as in example 1, and the results are shown in Table 1.
[ example 12 ]
16.4 g of ammonium tungstate, 1.05 g of rubidium nitrate and 3.42 g of sodium tantalate are weighed into 100 ml of deionized water, and 81 g of water having a specific surface area of 117m is added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with the aperture of 15nm to 3.5 by using 2.5% ammonia water, immersing 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 a drying oven at the temperature of 120 ℃ for 8 hours, putting the sample into a muffle furnace, and heating the sample at the temperature of 550 DEG CCalcining for 4 hours under the condition to obtain the required catalyst. The reaction conditions were the same as in example 1, and the results are shown in Table 1.
[ example 13 ]
16.4 g of ammonium tungstate, 1.38 g of cesium nitrate and 3.42 g of sodium tantalate were weighed and added to 100 ml of deionized water, and 81 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 reaction conditions were the same as in example 1, and the results are shown in Table 1.
[ example 14 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate were weighed, added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 15 ]
79 g of chromium nitrate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate are weighed into 100 ml of deionized water, and 81 g of specific surface area 117m is 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 16 ] A method for producing a polycarbonate
Weigh 16.4 grams of ammonium tungstate, 2.15 grams of potassium nitrate, 3.45 grams of vanadiumAmmonium sulfate, 6.08 g niobium oxalate, was added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 17 ]
16.4 g of ammonium tungstate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate were weighed in 100 ml of deionized water, and 81 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 the pore diameter of 15nm to 1 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 roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 18 ]
47.2 g of chromium oxalate, 2.15 g of potassium nitrate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate were weighed into 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 19 ] to provide
16.4 g of ammonium tungstate, 2.15 g of potassium nitrate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate were weighed and added to 100 ml of deionized water, and 81 g of a water having a specific surface area of 117m was added2G, pore diameter 15And (2) adjusting the pH value of the solution to 3 by using 2.5% ammonia water, soaking in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering, drying 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 20 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 6.9 g of ammonium vanadate were weighed, and the weighed materials were added to 100 ml of deionized water, followed by addition of 81 g of a specific surface area of 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 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 21 ] to provide
13.17 g of chromium nitrate, 2.73 g of ammonium tungstate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed, and the weighed materials were added to 100 ml of deionized water, followed by addition of 81 g of a specific surface area of 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 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 22 ]
65.83 g of chromium nitrate, 13.63 g of ammonium tungstate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 g of a specific surface area of 117m was added2Alumina carrier with pore diameter of 15nm, adjusting pH value of the solution to 3.5 with 2.5% ammonia water, soaking in 50 deg.C water bath for 1 hr, taking out sample, filtering, and drying in 120 deg.C ovenDrying 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 23 ]
26.33 g of chromium nitrate, 5.46 g of ammonium tungstate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed, and the weighed materials were added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 24 ]
52.66 g of chromium nitrate, 10.93 g of ammonium tungstate, 2.15 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed, and the weighed materials were added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 25 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 8.2 g of ammonium tungstate and 12.14 g of niobium oxalate were weighed, and the weighed materials were added to 100 ml of deionized water, followed by addition of 81 g of water having a specific surface area of 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 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. Reaction of propane material and the catalyst in a reaction stripThe reaction was carried out under the same conditions as in example 1, and the results are shown in Table 1.
[ example 26 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 8.2 g of ammonium tungstate and 3.42 g of sodium tantalate were weighed, and the weighed materials were added to 100 ml of deionized water, followed by addition of 81 g of water having a specific surface area of 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 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 27 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 8.2 g of ammonium tungstate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate were weighed, added to 100 ml of deionized water, and then 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 28 ]
15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate were weighed, added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 29 ] to
63.2 g of chromium nitrate, 3.28 g of ammonium tungstate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate were weighed, added to 100 ml of deionized water, and then 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 30 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 8.2 g of ammonium tungstate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate were weighed, added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 31 ]
15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 2.15 g of potassium nitrate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate were weighed, added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 32 ]
Weigh 63.2 grams of chromium nitrate, 3.28 grams of ammonium tungstate, 2.15 gramsPotassium nitrate, ammonium vanadate, 3.45 g and sodium tantalate, 1.71 g, were added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 33 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 8.2 g of ammonium tungstate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate were weighed, added to 100 ml of deionized water, and then 81 g of water having 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 34 ] A method for producing a polycarbonate
15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 2.15 g of potassium nitrate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate were weighed, and added to 100 ml of deionized water, 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 35 ]
Weigh 63.2 grams of chromium nitrate, 3.28 grams of ammonium tungstate, 2.15 grams of potassium nitrate, 2.3 grams of ammonium vanadate, 4.05 grams of niobium oxalate, 1.14 grams ofAdding sodium tantalate (81 g) into 100 ml of deionized water, and adding 117m of specific surface area (81 g)2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with the pore diameter of 15nm to 3.5 by using 2.5% ammonia water, then 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 then putting the sample into a muffle furnace to roast at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 36 ]
79 g of chromium nitrate, 0.22 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed into 100 ml of deionized water, and 81 g of a specific surface area of 117m was added2The method comprises the following steps of regulating the pH value of an alumina carrier with the pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering, 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 37 ]
79 g of chromium nitrate, 4.3 g of potassium nitrate and 6.9 g of ammonium vanadate were weighed into 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 38 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 g of a specific surface area of 117m was added2Alumina carrier with 15nm pore diameter, 2.5% ammonia water to regulate pH value to 3.5, and water at 50 deg.CAfter 1 hour of immersion in the bath, the sample was taken out and filtered, dried in an oven at 120 ℃ for 8 hours, and then calcined in a muffle furnace at 550 ℃ for 4 hours to obtain the desired catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 510 ℃; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 39 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 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 the pore diameter of 15nm to 3.5 by using 2.5% ammonia water, then 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 then putting the sample into a muffle furnace to roast at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 40 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 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 propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 660 ℃ temperature; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 41 ] to provide a pharmaceutical composition
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 g of a specific surface area of 117m was added2Alumina carrier with pore diameter of 15nm, adjusting pH value of the solution to 3.5 with 2.5% ammonia water, soaking in 50 deg.C water bath for 1 hr, and taking outAnd filtering the product, drying the product in a 120 ℃ oven for 8 hours, and then putting the sample into a muffle furnace to roast the sample for 4 hours at 550 ℃ to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: the pressure is 1MPa, and the temperature is 620 ℃; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 42 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 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 propane raw material reacts with the catalyst under the following reaction conditions: the pressure is 0.05MPa, and the temperature is 620 ℃; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 43 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 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 the pore diameter of 15nm to 3.5 by using 2.5% ammonia water, then 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 then putting the sample into a muffle furnace to roast at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 0.1h-1. The results are shown in Table 2.
[ example 44 ]
39.5 g of chromium nitrate, 2.15 g of potassium nitrate, 3.89 g of tungsten acetate and 2.3 g of ammonium vanadate were weighed, added to 100 ml of deionized water, and 81 g of a specific surface area of 117m was added2Alumina carrier with pore diameter of 15nm, regulating pH value of the solution to 3.5 with 2.5% ammonia water, soaking in 50 deg.C water bath for 1 hr, taking out sample, and filteringAnd 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 propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 9h-1. The results are shown in Table 2.
Comparative example 1
63.2 g of chromium nitrate and 3.28 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 2
Ammonium tungstate 16.4 g and potassium nitrate 2.15 g were weighed and added to 100 ml of deionized water, and then 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 3
16.4 g of ammonium tungstate was weighed, added to 100 ml of deionized water, and further added 81 g of ammonium tungstate having a specific surface area of 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 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 4
79 g of chromium nitrate, 0.68 g of sodium carbonate and 3.03 g of ferric nitrate are weighed into 100 ml of deionized water, and 81 g of a specific surface area of 117m are 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ COMPARATIVE EXAMPLE 5 ]
15.8 g of chromium nitrate and 13.12 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and then 81 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 propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
TABLE 1
[ examples 38 to 44 ]
The catalyst prepared in example 16 was used for propane dehydrogenation, and the reaction conditions and evaluation results are shown in Table 2.
TABLE 2
Claims (7)
1. A method for preparing propylene by propane dehydrogenation comprises the step of directly contacting and reacting a propane raw material with a catalyst to obtain propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 510-660 ℃, and the mass space velocity is 0.1-9 h-1(ii) a The catalyst comprises the following components in parts by weight:
a) 2-30 parts of oxides of two elements of Cr and W;
b)0 to 5 parts but not 0 part of an oxide of at least one element of the IA group;
c) 0.01-5 parts of a mixture of oxides of V, Nb and Ta in VB group of the periodic table;
d) 69-96 parts of Al2O3A carrier;
in the catalyst, the weight ratio of Cr to W is as follows: (0.1-9): 1.
2. the method for preparing propylene by propane dehydrogenation according to claim 1, wherein the amount of the oxide of Cr and W is 5-20 parts by weight based on the weight of the catalyst.
3. The method for preparing propylene by propane dehydrogenation according to claim 1, wherein the amount of the oxide of at least one element selected from group IA of the periodic table of elements is 0.01-3 parts by weight based on the weight of the catalyst, wherein the element of group IA is at least one selected from Li, Na, K, Rb and Cs.
4. The method for preparing propylene by propane dehydrogenation according to claim 1, wherein the amount of the mixture of the oxides of V, Nb and Ta in group VB of the periodic table is 0.01-3 parts by weight based on the weight of the catalyst.
5. The method for preparing propylene by propane dehydrogenation according to claim 1, wherein Al is2O3The specific surface area of the carrier is 50-500 m2The pore diameter is 5-40 nm.
6. The method for preparing propylene by dehydrogenation of propane according to claim 5, wherein Al is2O3The specific surface area of the carrier is 117-350 m2The pore diameter is 8-25 nm.
7. The method for preparing propylene by dehydrogenation of propane according to any of claims 1 to 6, wherein the method for preparing the catalyst comprises the following steps:
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 soluble solution containing Cr and W and soluble solutions in the IA group and the VB group of the periodic table in required amounts to form a mixture I, and adjusting the pH value of the mixture I to be 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 catalyst.
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