CN117920241A - Alkyl arene dehydrogenation catalyst and preparation method and application thereof - Google Patents
Alkyl arene dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN117920241A CN117920241A CN202211306066.4A CN202211306066A CN117920241A CN 117920241 A CN117920241 A CN 117920241A CN 202211306066 A CN202211306066 A CN 202211306066A CN 117920241 A CN117920241 A CN 117920241A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- -1 Alkyl arene Chemical class 0.000 title claims abstract description 34
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 26
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims abstract description 7
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 18
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 16
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 229910052700 potassium Inorganic materials 0.000 abstract description 11
- 239000011591 potassium Substances 0.000 abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 22
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 22
- 239000002245 particle Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 13
- 239000011609 ammonium molybdate Substances 0.000 description 13
- 229940010552 ammonium molybdate Drugs 0.000 description 13
- 235000018660 ammonium molybdate Nutrition 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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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 discloses an alkyl aromatic hydrocarbon dehydrogenation catalyst, a preparation method and application thereof. The catalyst comprises the following components in percentage by weight based on the mass of the catalyst: (a) 70% -80% of Fe 2O3; (b) 3 to 6 percent of K 2 O; (c) 6% -11% of CeO 2; (d) 0.5 to 5 percent of MoO 3; (e) 0.5% -5% BaO; (f) At least one selected from CoFe 2O4、NiFe2O4 and BiFeO 3, and the content is 0.8-7.7%. The catalyst has low potassium content, is used for preparing the alkenyl arene by dehydrogenating the alkyl arene at a high airspeed, has good activity and stability, and has high yield, so that the material consumption and the energy consumption of unit products are effectively reduced, the running period of the device can be prolonged, the updating cost of the catalyst and the yield loss caused by frequent replacement of the catalyst are reduced.
Description
Technical Field
The invention belongs to the field of alkyl arene dehydrogenation, and particularly relates to an alkyl arene dehydrogenation catalyst, a preparation method and application thereof.
Background
The industrial alkyl alkenyl arene is mainly prepared by dehydrogenating alkyl arene, and one of the key points of the method is to select a dehydrogenation catalyst with high activity, high selectivity and good stability. Iron-based catalysts using iron oxide as a main active component and potassium oxide as a main promoter are commonly used as alkyl aromatic hydrocarbon dehydrogenation catalysts. Usually, the potassium content is more than 12wt%, but the potassium is not stable enough, is easy to run off and migrate under the flushing of high-temperature steam, influences the self-regeneration capability and stability of the catalyst, is one of the main reasons for irreversible deactivation of the catalyst, and realizes the aim of development of low potassium content within 7 wt%.
Existing iron-based catalysts are mainly divided into two categories: one type is an alkylaromatic dehydrogenation catalyst of the Fe-K-Cr series. The catalysts are disclosed in CN87100517A, and have better activity and stability, but are eliminated due to the chromium with heavy environmental pollution; the other is an alkylaromatic dehydrogenation catalyst of the Fe-K-Ce-Mo series. Cn201210021958.X discloses a high cerium content alkylaromatic dehydrogenation catalyst and a method for making the same. CN201010245943.2 discloses a dehydrogenation catalyst using micron-sized ferric oxide and potassium carbonate as raw materials. The catalyst not only replaces Cr with Ce and Mo (or W), but also has greatly improved activity compared with the former catalyst, but the catalyst has high K 2 O content, generally 8-25 wt%, insufficient space velocity of 1.0-1.5 h -1 and relatively high water ratio (weight) of 2.0.
The method has the advantages that the potential of the device is excavated to obtain as many alkenyl arene products as possible, the production cost is reduced, the benefit is maximized, the feeding amount of a plurality of alkenyl arene devices is more than 120 percent of the design value, and high requirements are put on the high airspeed resistance of the catalyst. The development of a high space velocity catalyst suitable for isothermal fixed beds with a water ratio below 1.6 (by weight) to obtain as much alkenyl arene product as possible, and at the same time, reduce unit energy consumption and material consumption, enhance competitiveness, and become urgent need for many devices, especially large-scale devices, both at sea and abroad. Therefore, the use condition of the dehydrogenation catalyst is slightly improved, and the investment is slightly increased, so that the production enterprises can obtain great economic benefits. It has been a direction of efforts by researchers to develop a low potassium catalyst suitable for operation at high space velocity, having higher activity and better stability.
Disclosure of Invention
Aiming at the problems of low activity and poor stability of the alkyl aromatic hydrocarbon dehydrogenation catalyst with low potassium content under the high space velocity condition in the prior art, the invention provides an alkyl aromatic hydrocarbon dehydrogenation catalyst and a preparation method and application thereof. The catalyst has low potassium content, is used for preparing the alkenyl arene by dehydrogenating the alkyl arene at a high airspeed, has good activity and stability, and has high yield, so that the material consumption and the energy consumption of unit products are effectively reduced, the running period of the device can be prolonged, the updating cost of the catalyst and the yield loss caused by frequent replacement of the catalyst are reduced.
The invention provides an alkyl aromatic hydrocarbon dehydrogenation catalyst, which comprises the following components in percentage by weight based on the mass of the catalyst:
(a) 70% -80% of Fe 2O3;
(b) 3 to 6 percent of K 2 O;
(c) 6% -11% of CeO 2;
(d) 0.5 to 5 percent of MoO 3;
(e) 0.5% -5% of BaO;
(f) At least one selected from CoFe 2O4、NiFe2O4 and BiFeO 3, and the content is 0.8-7.7%.
According to the invention, the content of component (f) is 1.5% to 6.5%.
According to the present invention, component (f) is at least two selected from CoFe 2O4、NiFe2O4 and BiFeO 3. Preferably, component (f) is a composition comprising both CoFe 2O4 and at least one selected from NiFe 2O4、BiFeO3. Further preferably, the mass ratio of CoFe 2O4 to at least one selected from NiFe 2O4、BiFeO3 is (1 to 10): 1.
According to the invention, preferably, the catalyst further comprises component (g); the component (g) is at least one selected from Ta 2O5、Nb2O5 and V 2O5, and the content of the component (g) is 0.5-5%. Further preferably, component (g) is any two selected from Ta 2O5、Nb2O5 and V 2O5; such as comprising both Ta 2O5 and Nb 2O5, or Ta 2O5 and V 2O5, or Nb 2O5 and V 2O5, which have a binary synergy in enhancing the activity of the low potassium content catalyst at high space velocities. Still more preferably, component (g) is a composition comprising both Ta 2O5、Nb2O5 and V 2O5, in which case the three oxides have a ternary synergy in enhancing the activity of the low potassium content catalyst at high space velocities.
According to the present invention, preferably, the catalyst does not contain a binder.
According to the present invention, preferably, the catalyst does not contain tungsten oxide.
According to the invention, in the H 2 -TPR spectrum, the initial reduction temperature of the catalyst is 380-410 ℃, and the complete reduction temperature/initial reduction temperature is 1.98-2.2.
The second aspect of the present invention provides a method for preparing the above catalyst, comprising the steps of: mixing a Fe source, a K source, a Ce source, a Mo source, a Ba source, at least one selected from a Co source, a Ni source and a Bi source, and a pore-forming agent, and roasting to obtain the catalyst.
According to the present invention, the Fe source comprises at least one of iron oxide red and iron oxide yellow, preferably iron oxide red and iron oxide yellow, and more preferably iron oxide red and iron oxide yellow, in a weight ratio of (1.0 to 4.0): 1. And/or, the K source comprises potassium carbonate; and/or the Ce source comprises at least one of cerium acetate and cerium carbonate. And/or, the Mo source comprises at least one of a salt, an oxide of Mo; and/or, the Ba source comprises at least one of oxide and carbonate. And/or, the Co source comprises CoFe 2O4. And/or, the Ni source comprises NiFe 2O4. And/or, the Bi source comprises BiFeO 3.
According to the present invention, at least one selected from the group consisting of Ta source, nb source and V source is further included in the catalyst raw material. At least one selected from the group consisting of Ta source, nb source and V source is mixed and added together with Fe source, K source, ce source, mo source, ba source and pore-forming agent. And/or, the Ta source is added in oxide form. And/or, the Nb source is added in the form of an oxide. And/or, the V source is added in oxide form.
According to the invention, the porogen comprises at least one of graphite, polystyrene microspheres and sodium carboxymethyl cellulose. The addition amount of the pore-forming agent is 3.1 to 6.6 percent of the total weight of the catalyst.
According to the invention, the mixing time of the source of Fe, the source of K, the source of Ce, the source of Mo, the source of Ba, at least one selected from the source of Co, the source of Ni and the source of Bi and the pore-forming agent is 0.5 to 1.5 hours. Preferably, the Fe source, the K source, the Ce source, the Mo source, the Ba source and the pore-forming agent are mixed and stirred for 40-60 min, and then at least one selected from the Co source, the Ni source and the Bi source is added.
According to the invention, no binder is included in the catalyst feedstock. The binder comprises at least one of kaolin, diatomite, cement, montmorillonite, halloysite, quasi halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
According to the invention, the preparation method comprises an optional shaping and an optional drying step before calcination.
According to the invention, a proper amount of water can be added as required in the molding process. Preferably, the water is added in an amount of 21 to 39% by weight based on the total weight of the catalyst.
According to the present invention, the drying temperature is not particularly limited. Preferably, the drying temperature is 45 to 125 ℃. And/or preferably, the drying time is 3 to 8 hours. Preferably, the drying is carried out by a two-step method, namely, drying at 45-85 ℃ for 0.5-1.5 h and drying at 100-125 ℃ for 2.5-4.5 h.
According to the present invention, the firing temperature is not particularly limited. Preferably, the firing temperature is 580 to 905 ℃. And/or preferably, the roasting time is 4-8 h. As a preferred choice, the roasting adopts a two-step method, namely, roasting at 585-685 ℃ for 1.5-2.5 h and roasting at 835-905 ℃ for 2.5-3.5 h.
The third aspect of the invention provides an application of the catalyst or the catalyst prepared by the preparation method in the reaction of preparing alkenyl arene by dehydrogenating alkyl arene.
According to the invention, the application is dehydrogenation at high space velocities. The liquid volume space velocity is 2.0-4.0 h -1.
According to the invention, alkyl aromatic hydrocarbon is used as a raw material, and the raw material is contacted and reacted with the catalyst to obtain the alkenyl aromatic hydrocarbon. The alkyl aromatic hydrocarbon comprises at least one of ethylbenzene, methyl ethylbenzene, diethyl benzene and the like.
According to the invention, the temperature of the reaction is 600-630 ℃; and/or the water ratio (weight) is 1.0-1.6; and/or the reaction pressure is-70 to-50 KPa.
Compared with the prior art, the invention has the following advantages:
1. In the catalyst, a proper amount of at least one selected from CoFe 2O4、NiFe2O4 and BiFeO 3 is added into an iron-potassium-cerium-molybdenum-barium catalytic system, and particularly at least one selected from Ta 2O5、Nb2O5 or V 2O5 is added, so that on one hand, the electron transfer capacity of an active phase is improved, more raw materials are treated, higher activity is obtained, on the other hand, the introduction of low-efficiency substances is reduced, the alkalinity of the system is improved, the active phase of the catalyst is stabilized and dispersed, the water gas reaction rate of water vapor and catalyst surface area carbon is accelerated, the self-regeneration capacity of the catalyst is enhanced, and the activity and stability of the catalyst with low potassium content under the condition of high airspeed are obviously improved.
2. In the preparation method of the catalyst, the steps of the method are simple, and the prepared catalyst is suitable for preparing the alkenyl arene by dehydrogenating the alkyl arene under the conditions of high space velocity and low water ratio. The catalyst has high activity and good stability.
3. In the application of the catalyst, the catalyst is suitable for preparing the alkenyl arene by dehydrogenating the alkyl arene under the conditions of high space velocity and low water ratio. The catalyst has high activity and good stability. The catalyst provided by the invention has the advantages that the ethylbenzene conversion rate can reach 73.7% under the conditions of-65 KPa, ethylbenzene volume space velocity of 2.5 hours -1, reaction temperature of 610 ℃ and water/ethylbenzene weight ratio of 1.3, and the ethylbenzene conversion rate is only reduced by 0.2% after the catalyst is operated for 1100 hours, so that a better technical effect is obtained.
Drawings
FIG. 1 is a graph of H 2 -TPR for the catalyst of example 1;
FIG. 2 is a graph of the H 2 -TPR profile of the catalyst of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples:
in the present invention, the catalysts of examples and comparative examples were evaluated for activity in an isothermal fixed bed.
In the present invention, the evaluation of the alkyl aromatic hydrocarbon dehydrogenation reaction is exemplified by the reaction of preparing styrene by ethylbenzene dehydrogenation. For the evaluation of the activity of the catalyst for preparing styrene by ethylbenzene dehydrogenation, the process is briefly described as follows:
Deionized water and ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gaseous state, and then enter into a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reactor was internally filled with 100 ml of a catalyst having a particle diameter of 3mm, which was a stainless steel tube having an inner diameter of 1 ". The reaction product flowing out of the reactor was condensed and analyzed for its composition by gas chromatography.
The ethylbenzene conversion and styrene selectivity were calculated according to the following formula:
The change of the reduction temperature of the catalyst was observed by temperature-programmed reduction (H 2 -TPR), 50mg of the catalyst sample was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature of 20℃and switched to H 2/N2 reducing gas for temperature-programmed reduction, and heated to 850℃at a rate of 10℃per minute.
In the present invention, the content of the raw materials in Table 1 is calculated in parts by weight.
[ Example 1]
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 1.68 parts of Ta 2O5 and 5.21 parts of sodium carboxymethylcellulose are stirred in a kneader for 0.75 hour, 2.56 parts of CoFe 2O4 and 0.78 part of NiFe 2O4 are added, stirring is carried out for 0.75 hour again, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hour, extruded strips are taken out, extruded into particles with the diameter of 3mm and the length of 6mm, the particles are put into an oven, baked for 0.75 hour at 65 ℃, baked for 3 hours at 115 ℃, then the oven is baked for 2 hours at 615 ℃, the temperature of 895 ℃ to obtain a finished catalyst, and the catalyst composition shown in Table 1 is obtained.
The H 2 -TPR profile of the catalyst of example 1 is shown in FIG. 1.
100 Ml of the catalyst was charged into the reactor, and the activity was evaluated at-65 KPa, a liquid ethylbenzene volume space velocity of 2.5 hours -1, a reaction temperature of 610℃and a water/ethylbenzene weight ratio of 1.3, and the test results are shown in Table 2.
[ Examples 1 to 1]
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO and 5.21 parts of sodium carboxymethyl cellulose are stirred in a kneader for 0.75 hours, 2.56 parts of CoFe 2O4 and 0.78 parts of NiFe 2O4 are added, stirring is carried out for 0.75 hours again, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hours, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6mm, the particles are put into an oven, baked for 0.75 hours at 65 ℃, baked for 3 hours at 115 ℃, then the obtained finished catalyst is obtained by baking for 2 hours at 615 ℃ and baked for 3 hours at 895 ℃, and the composition of the catalyst is listed in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Examples 1-2]
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO and 5.21 parts of sodium carboxymethyl cellulose are stirred in a kneader for 0.75 hour, 2.56 parts of CoFe 2O4 are added, stirred for 0.75 hour again, deionized water accounting for 29.5 percent of the total weight of the catalyst raw materials is added, stirred for 0.5 hour, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6mm, the particles are put into an oven, baked for 0.75 hour at 65 ℃ and baked for 3 hours at 115 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 615 ℃ and baked for 3 hours at 895 ℃ to obtain a finished catalyst, the composition of which is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 2]
The catalyst preparation method and the catalyst evaluation conditions and analysis method were the same as in example 1, except that Nb 2O5 was used instead of Ta 2O5, and the specific composition was:
58.7 parts of Fe 2O3's iron oxide red, 17.2 parts of Fe 2O3's iron oxide yellow, 5.11 parts of K 2 O's potassium carbonate, 8.67 parts of CeO 2's cerium carbonate, 2.77 parts of MoO 3's ammonium molybdate, 2.53 parts of BaO's barium carbonate, 2.56 parts of CoFe 2O4, 0.78 parts of NiFe 2O4, 1.68 parts of Nb 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 3]
The catalyst preparation method and catalyst evaluation conditions and analysis method were the same as in example 1, except that V 2O5 was used instead of Ta 2O5,BiFeO3 for NiFe 2O4, and the specific composition was:
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 2.56 parts of CoFe 2O4, 0.78 parts of BiFeO 3, 1.68 parts of V 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 4]
A catalyst was prepared, evaluated, and analyzed as in example 1, except that 0.84 parts of Ta 2O5 and 0.84 parts of Nb 2O5 were used in place of 1.68 parts of Ta 2O5, with the following specific composition:
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 2.56 parts of CoFe 2O4, 0.78 part of NiFe 2O4, 0.84 part of Ta 2O5, 0.84 part of Nb 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 5]
A catalyst was prepared, evaluated, and analyzed as in example 1, except that 0.84 parts Ta 2O5 and 0.84 parts V 2O5 were used instead of 1.68 parts Ta 2O5,BiFeO3 for substituting NiFe 2O4, with the specific composition:
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 2.56 parts of CoFe 2O4, 0.78 parts of BiFeO 3, 0.84 parts of Ta 2O5, 0.84 parts of V 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 6]
A catalyst was prepared, evaluated, and analyzed as in example 1, except that 0.84 parts Nb 2O5 and 0.84 parts V 2O5 were used in place of 1.68 parts Ta 2O5, with the following specific composition:
Iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 2.56 parts of CoFe 2O4, 0.78 part of NiFe 2O4, 0.84 part of Nb 2O5, 0.84 part of V 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 7]
A catalyst was prepared, evaluated, and analyzed as in example 1, except that 0.56 parts of TaO 2, 0.56 parts of Nb 2O5, and 0.56 parts of V 2O5 were used in place of 1.68 parts of Ta 2O5, with the following specific composition:
iron oxide red corresponding to 58.7 parts of Fe 2O3, iron oxide yellow corresponding to 17.2 parts of Fe 2O3, potassium carbonate corresponding to 5.11 parts of K 2 O, cerium carbonate corresponding to 8.67 parts of CeO 2, ammonium molybdate corresponding to 2.77 parts of MoO 3, barium carbonate corresponding to 2.53 parts of BaO, 2.56 parts of CoFe 2O4, 0.78 parts of NiFe 2O4, 0.56 parts of TaO 2, 0.56 parts of Nb 2O5, 0.56 parts of V 2O5 and 5.21 parts of sodium carboxymethyl cellulose. The catalyst composition is shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 8]
56.61 Parts of Fe 2O3 iron oxide red, 14.25 parts of Fe 2O3 iron oxide yellow, 3.35 parts of K 2 O potassium carbonate, 10.9 parts of CeO 2 cerium carbonate, 4.16 parts of MoO 3 ammonium molybdate, 3.35 parts of BaO barium carbonate, 0.92 part of Ta 2O5, 0.51 part of ZrO 2 and 4.87 parts of graphite are stirred in a kneader for 0.75 hours, 3.51 parts of CoFe 2O4 and 2.44 parts of NiFe 2O4 are added, stirring is carried out for 0.75 hours, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hours, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6mm, the particles are put into an oven, the oven is baked for 0.75 hours at 65 ℃, the temperature of 115 ℃ for 3 hours, the oven is baked for 2 hours at 615 ℃ and the temperature of 895 ℃ for obtaining a finished catalyst, and the catalyst, the composition shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 9]
Iron oxide red corresponding to 40.84 parts of Fe 2O3, iron oxide yellow corresponding to 36.9 parts of Fe 2O3, potassium carbonate corresponding to 4.55 parts of K 2 O, cerium acetate corresponding to 7.55 parts of CeO 2, ammonium molybdate corresponding to 1.72 parts of MoO 3, barium carbonate corresponding to 4.9 parts of BaO, 2.59 parts of Ta 2O5 and 4.87 parts of graphite are stirred in a kneader for 0.75 hours, 0.79 parts of CoFe 2O4 and 0.16 parts of NiFe 2O4 are added, stirring is carried out for 0.75 hours again, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hours, extruded strips are taken out, extruded into particles with the diameter of 3mm and the length of 6 mm, the particles are put into an oven, baked for 0.75 hours at 65 ℃, then put into a muffle furnace for 3 hours, baked for 2 hours at 615 ℃, and baked for 3 hours at 895 ℃ to obtain a finished product, and the catalyst, the composition shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 10]
Iron oxide red corresponding to 60.59 parts of Fe 2O3, iron oxide yellow corresponding to 17.46 parts of Fe 2O3, potassium carbonate corresponding to 3.32 parts of K 2 O, cerium carbonate corresponding to 6.15 parts of CeO 2, ammonium molybdate corresponding to 0.6 parts of MoO 3, barium carbonate corresponding to 0.55 parts of BaO, 3.83 parts of Ta 2O5 and 5.21 parts of sodium carboxymethylcellulose are stirred in a kneader for 0.75 hours, 6.7 parts of CoFe 2O4 and 0.8 part of NiFe 2O4 are added, stirring is carried out for 0.75 hours again, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hours, extruded into particles with the diameter of 3 mm and the length of 6mm, the particles are put into an oven, baked for 0.75 hours at the temperature of 65 ℃, baked for 3 hours at the temperature of 115 ℃, then baked for 2 hours at the temperature of 615 ℃, and baked for 3 hours at the temperature of 895 ℃ to obtain a finished catalyst, and the catalyst composition shown in Table 1.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ Example 11]
Iron oxide red corresponding to 54.7 parts of Fe 2O3, iron oxide yellow corresponding to 25.2 parts of Fe 2O3, potassium carbonate corresponding to 4.05 parts of K 2 O, cerium carbonate corresponding to 7.25 parts of CeO 2, ammonium molybdate corresponding to 1.67 parts of MoO 3, barium carbonate corresponding to 1.38 parts of BaO, 0.89 part of V 2O5 and 5.21 parts of sodium carboxymethylcellulose are stirred in a kneader for 0.75 hour, 4.05 parts of CoFe 2O4 and 0.81 part of NiFe 2O4 are added, stirring is carried out for 0.75 hour again, deionized water accounting for 29.5% of the total weight of the catalyst raw materials is added, stirring is carried out for 0.5 hour, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6mm, the particles are put into an oven, baked for 0.75 hour at 65 ℃, baked for 3 hours at 115 ℃, then the oven is baked for 2 hours at 615 ℃, the temperature of 895 ℃ to obtain a finished catalyst, and the catalyst composition shown in Table 1 is obtained.
The catalysts were evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 1
The catalyst was prepared, evaluated and analyzed as in example 1, except that 0.99 parts of WO 3 was also added, the catalyst composition is shown in Table 1, and the test results are shown in Table 2. The H 2 -TPR spectrum of the catalyst of this example is shown in FIG. 2.
TABLE 1
Table 1 (Xue 1)
TABLE 2
The above examples illustrate that adding a proper amount of CoFe 2O4、NiFe2O4 or BiFeO 3 and at least one selected from Ta 2O5、Nb2O5 or V 2O5 to an iron-potassium-cerium-molybdenum-barium catalytic system, without adding a binder, improves the activity and stability of the low-potassium catalyst under the condition of high space velocity, obviously enhances the reduction resistance of the catalyst, can greatly improve the feeding amount of the device, reduces the energy consumption and material consumption of unit products, contributes to the cost reduction and efficiency improvement of the device, and is a novel high space velocity catalyst which is worth recommending.
Claims (12)
1. The alkyl arene dehydrogenating catalyst consists of the following components in weight percent based on the mass of the catalyst:
(a) 70% -80% of Fe 2O3;
(b) 3 to 6 percent of K 2 O;
(c) 6% -11% of CeO 2;
(d) 0.5 to 5 percent of MoO 3;
(e) 0.5% -5% of BaO;
(f) At least one selected from CoFe 2O4、NiFe2O4 and BiFeO 3, and the content is 0.8-7.7%.
2. The catalyst of claim 1, wherein the catalyst further comprises component (g); the component (g) is at least one selected from Ta 2O5、Nb2O5 and V 2O5, and the content of the component (g) is 0.5-5%;
Preferably, component (g) is any two selected from Ta 2O5、Nb2O5 and V 2O5; more preferably, component (g) is a composition comprising both Ta 2O5、Nb2O5 and V 2O5.
3. The catalyst of claim 1 wherein component (f) is at least two selected from CoFe 2O4、NiFe2O4 and BiFeO 3;
Preferably, component (f) is a composition comprising both CoFe 2O4 and at least one selected from NiFe 2O4、BiFeO3;
Further preferably, the mass ratio of CoFe 2O4 to at least one selected from NiFe 2O4、BiFeO3 is (1 to 10): 1.
4. The catalyst of claim 1, wherein in the H 2 -TPR profile, the catalyst has an initial reduction temperature of 380 to 410 ℃ and a full reduction temperature/initial reduction temperature of 1.98 to 2.2.
5. The catalyst of any one of claims 1 to 4, wherein the catalyst is free of tungsten oxide.
6. The method for preparing the catalyst according to any one of claims 1 to 5, comprising the steps of: mixing a Fe source, a K source, a Ce source, a Mo source, a Ba source, at least one selected from a Co source, a Ni source and a Bi source, and a pore-forming agent, and roasting to obtain the catalyst.
7. The production method according to claim 6, wherein the Fe source comprises at least one of iron oxide red and iron oxide yellow, preferably iron oxide red and iron oxide yellow, more preferably iron oxide red and iron oxide yellow, in a weight ratio of (1.0 to 4.0): 1, a step of;
and/or, the K source comprises potassium carbonate;
and/or, the Ce source comprises at least one of cerium acetate and cerium carbonate;
And/or, the Mo source comprises at least one of a salt, an oxide of Mo;
And/or, the Ba source comprises at least one of oxide and carbonate;
And/or, the Co source comprises CoFe 2O4;
And/or, the Ni source comprises NiFe 2O4;
And/or, the Bi source comprises BiFeO 3.
8. The method according to claim 6, wherein the catalyst material further comprises at least one selected from the group consisting of a Ta source, a Nb source and a V source; at least one selected from the group consisting of Ta source, nb source and V source is mixed and added together with Fe source, K source, ce source, mo source, ba source and pore-forming agent.
9. The preparation method according to claim 6, wherein the mixing time of the pore-forming agent and at least one of a Fe source, a K source, a Ce source, a Mo source, a Ba source, a Co source, a Ni source and a Bi source is 0.5 to 1.5 hours; preferably, the Fe source, the K source, the Ce source, the Mo source, the Ba source and the pore-forming agent are mixed and stirred for 40-60 min, and then at least one selected from the Co source, the Ni source and the Bi source is added.
10. Use of the catalyst according to any one of claims 1 to 5 or the catalyst prepared by the preparation method according to any one of claims 6 to 9 in a reaction for preparing an alkenyl arene by dehydrogenation of an alkyl arene.
11. The use according to claim 10, characterized in that the use is a dehydrogenation reaction at high space velocity; the liquid volume space velocity is 2.0-4.0 h -1.
12. The use according to claim 10, wherein the temperature of the reaction is 600-630 ℃; and/or, the water ratio is 1.0 to 1.6 by weight; and/or the reaction pressure is-70 to-50 KPa.
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