CN112239389B - Process for producing alkalkenyl aromatic hydrocarbon - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 157
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 27
- -1 alkyl alkenyl arene Chemical class 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 21
- 239000011591 potassium Substances 0.000 claims abstract description 21
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 101
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 13
- 229960001759 cerium oxalate Drugs 0.000 claims description 12
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 68
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 42
- 239000000203 mixture Substances 0.000 description 42
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 21
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 20
- 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 18
- 239000001768 carboxy methyl cellulose Substances 0.000 description 18
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 18
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 18
- 239000011148 porous material Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229920002223 polystyrene Polymers 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
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 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
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- 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
- 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
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/613—
-
- B01J35/647—
-
- 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
- C07C2523/888—Tungsten
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing alkyl alkenyl arene, which mainly solves the problems of low activity and poor stability of low-potassium catalyst under low temperature condition in the prior art. The method comprises the steps of carrying out dehydrogenation reaction on alkyl aromatic hydrocarbon serving as a raw material in the presence of an ultralow-potassium catalyst to obtain alkyl alkenyl aromatic hydrocarbon; wherein the reaction temperature is 580-600 ℃, and the liquid space velocity is 0.5-1.5 hours －1 The water ratio (weight) is 1.0-2.0, and the pressure is-40 KPa-normal pressure; the ultra-low potassium catalyst comprises: iron, potassium, cerium and 0.5-5% of WO 3 (ii) a The technical proposal of 0.5 to 5 percent of CaO better solves the problem and can be used in the industrial production of preparing the alkyl alkenyl arene by dehydrogenating the alkyl arene.
Description
Technical Field
The invention relates to a low-temperature alkyl aromatic dehydrogenation catalyst with ultralow potassium content and a preparation method thereof.
Background
The industrial alkyl alkenyl arene is prepared mainly through catalytic dehydrogenation of alkyl arene, and the key point of the process is to select one kind of dehydrogenation catalyst with high activity, high selectivity and high stability. The catalysts reported in the patent fall into two categories: one is the Fe-K-Cr series, such as published U.S. Pat. Nos. 4152300, 4144197, and Chinese patent No. 87100517 alkyl aromatic dehydrogenation catalysts, although the activity and stability of the catalysts are better, the catalysts are eliminated because they contain chromium which is not environment-friendly. Another is Fe-K-Ce-Mo series, such as published Chinese patent 201210021958.X a high cerium content alkyl aromatic dehydrogenation catalyst and its preparation methodThe Chinese patent 200880018406.5 contains an indium dehydrogenation catalyst, and preparation and application thereof, the catalyst not only replaces Cr with Ce and Mo, but also has greatly improved activity and stability compared with the former catalyst, and the main problem of the catalyst is that K is 2 The content of O is high and is generally 10 to 20 percent.
The dehydrogenation catalyst for alkyl aromatic hydrocarbon is iron catalyst with ferric oxide as main active component and potassium oxide as main cocatalyst. However, potassium is slowly lost and migrated under the flushing of high-temperature steam, which is one of the main reasons for irreversible deactivation of the catalyst, and currently, the reduction of the potassium content is the mainstream of the development of the ethylbenzene dehydrogenation catalyst.
For the industrial production of styrene by ethylbenzene dehydrogenation, the annual output is mostly more than 10 ten thousand tons/year, more than 50 ten thousand tons/year scale devices are arranged in China, the high reaction temperature causes more byproducts, the energy consumption is high, and the problem troubling styrene manufacturers is always solved. If the dehydrogenation reaction temperature can be reduced by 5 ℃ to 10 ℃, for industrial devices, no equipment is required to be changed, investment is not required to be increased, a large amount of expenditure on water vapor and electricity can be saved in one year, and in addition, the dehydrogenation reaction is operated at low temperature, so that the method has positive significance for prolonging the service life of the catalyst and reducing the high temperature resistance requirement of equipment materials. Therefore, the development of an ultralow-potassium catalyst which is suitable for running under low-temperature conditions and has higher activity and better stability and the great reduction of energy consumption are always the directions of researchers.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a novel method for producing an alkalkenyl aromatic hydrocarbon, which is a problem of low activity and poor stability of the low-potassium alkyl aromatic hydrocarbon dehydrogenation catalyst under low temperature conditions in the prior art. The catalyst has ultra-low potassium content, has good low-temperature activity and stability when being used for preparing the alkyl alkenyl arene by dehydrogenating the alkyl arene, and can be used at a lower reaction temperature, thereby effectively reducing energy consumption, prolonging the operation period of a device, reducing the updating cost of the catalyst and reducing the yield loss caused by frequently replacing the catalyst.
The second technical problem to be solved by the present invention is to provide a preparation method of a low temperature alkyl aromatic dehydrogenation catalyst with ultra-low potassium content corresponding to the first technical problem.
The invention aims to solve the technical problem and provides a method for preparing the alkyl alkenyl arene by dehydrogenating the alkyl arene with ultralow potassium content at low temperature, which corresponds to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
a method for producing an alkyl-alkenyl aromatic hydrocarbon comprises a step of obtaining an alkyl-alkenyl aromatic hydrocarbon by subjecting an alkyl-aromatic hydrocarbon as a raw material to a dehydrogenation reaction in the presence of an ultra-low potassium catalyst; wherein the reaction temperature is 580-600 ℃, and the liquid space velocity is 0.5-1.5 hours －1 The water ratio (weight) is 1.0-2.0, and the pressure is-40 KPa-normal pressure; the ultra-low potassium catalyst comprises the following components in percentage by weight: (a) 66-79% of Fe 2 O 3 (ii) a (b) 2 to 6 percent of K 2 O; (c) 6 to 12 percent of CeO 2 (ii) a (d) 0.5 to 5 percent of WO 3 (ii) a (e) 0.5 to 5 percent of CaO;
the average pore diameter of the ultra-low potassium catalyst is 37.8-45.4 nm, and the specific surface area is 1.8-2.4 m 2 /g。
In the technical scheme, the catalyst also comprises (f) 0.5-8 wt% of MgFe 2 O 4 (ii) a (g) Selected from MnO 2 、ZrO 2 Or TiO 2 0.5 to 5% by weight of at least one of (A) and (B).
In the above technical scheme, the component (g) preferably also comprises MnO 2 And ZrO 2 Or MnO with 2 And TiO 2 Or ZrO 2 And TiO 2 The two oxides have a binary synergistic effect in the aspect of improving the low-temperature activity of the ultra-low potassium content catalyst; said (g) component preferably also comprises MnO 2 、ZrO 2 And TiO 2 2 At the moment, the three oxides have a ternary synergistic effect on the aspect of improving the low-temperature activity of the ultra-low potassium-content catalyst.
In the technical scheme, mgFe 2 O 4 The content is preferably 1 to 7%, more preferably 2 to 6%.
In the above technical scheme, by weight percentage, fe 2 O 3 Preferably from iron oxide red and iron oxide yellow, and the proportion is preferably iron oxide red: iron oxide yellow =2.0 to 3.2.
In the technical scheme, the catalyst preferably does not contain a binder, and the binder comprises kaolin, diatomite and cement.
In the above technical solution, the catalyst preferably does not contain molybdenum oxide.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps: mixing Fe source, K source, ce source, W source, ca source and MgFe according to a certain proportion 2 O 4 And is selected from MnO 2 、ZrO 2 Or TiO 2 The catalyst is obtained by uniformly contacting at least one of the pore-forming agent and water, extruding, drying and roasting. Preferably, the amount of water added is 19 to 38% by weight of the total catalyst feed.
In the above technical scheme, ce is preferably added in the form of cerium oxalate or cerium hydroxide.
In the technical scheme, the drying adopts two steps of 80-120 ℃ and 130-160 ℃, and the drying time is 1-3 hours and 2-6 hours respectively.
In the technical scheme, the roasting temperature can be 700-1000 ℃, and the roasting time can be 2-8 hours.
In the above technical scheme, the calcination temperature is preferably increased gradually, for example, but not limited to, 700-800 ℃ for 1-4 hours, and then 900-1000 ℃ for 1-4 hours.
In order to solve the third technical problem, alkyl aromatic hydrocarbon is used as raw material, the reaction temperature is 560-600 ℃, the dosage of the catalyst is 50-150 ml, and the liquid airspeed is 0.5-1.5 hours －1 The water ratio (weight) is 1.0-2.0, the pressure is-40 KPa-normal pressure, and the raw material and the alkyl arene dehydrogenation catalyst are contacted and reacted to obtain the alkyl alkenyl arene.
The catalyst component of the present invention uses the following raw materials:
the K is added in the form of potassium carbonate; w used is added in the form of its salt or oxide; the Ca is added in the form of oxide or carbonate; the rest of the elements are added in the form of salts or oxides thereof; in the preparation process of the invention, besides the main components of the catalyst, a pore-forming agent is added, wherein the pore-forming agent can be selected from graphite, polystyrene microspheres and sodium carboxymethyl cellulose, and the addition amount of the pore-forming agent is 2-6% of the total weight of the catalyst.
The pore distribution and specific surface area of the catalyst are determined by TriStar model 3000 physical adsorption instrument, and the pore diameter measuring range
The specific surface area is more than or equal to 0.01m 2 /g。
The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed, and for the activity evaluation of the catalyst for preparing styrene by ethylbenzene dehydrogenation, the process is briefly described as follows:
the deionized water and the ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gas state, and then the gas state enters a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reactor was a 1 "internal diameter stainless steel tube filled with 100 ml of a catalyst having a particle size of 3 mm. The composition of the reactants exiting the reactor was analyzed by gas chromatography after condensation of water.
The ethylbenzene conversion and the styrene selectivity are calculated according to the following formulas:
the determination of the pore size, the distribution and the specific surface area of the catalyst is completed on a TriStar 3000 type physical adsorption instrument by adopting a nitrogen adsorption method, and the pore diameter measurement range
Specific surface areaThe product is more than or equal to 0.01m 2 /g。
The invention adds proper amount of magnesium ferrite and MnO into the Fe-K-Ce-W-Ca catalyst system 2 、ZrO 2 Or TiO 2 The obtained catalyst has an average pore diameter of 37.8-45.4 nm and a proper specific surface area, on one hand, the electron transfer capacity of an active phase is improved, the higher activity is favorably obtained, on the other hand, the introduction of low-efficiency substances is reduced, the alkalinity of a system is improved, the active phase of the catalyst is stabilized and dispersed, the rate of water gas reaction between water vapor and carbon deposit on the surface of the catalyst is accelerated, the self-regeneration capacity of the catalyst is enhanced, the activity and the stability of the catalyst with ultra-low potassium content under the low-temperature condition are obviously improved, and the catalyst has the air speed of 1.2 hours under normal pressure and ethylbenzene -1 And under the conditions of reaction temperature of 590 ℃ and water/ethylbenzene weight ratio of 1.6, the ethylbenzene conversion rate reaches 68.3 percent, and the ethylbenzene conversion rate is only reduced by 0.5 percent after 2000 hours of operation, so that a better technical effect is obtained.
Drawings
FIG. 1 is a graph of the pore distribution of the catalyst of the present invention.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1]
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Cerium oxalate equivalent to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 1.68 parts of MnO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1. The catalysis is measured by adopting TriStar model 3000 physical adsorption instrumentPore distribution and specific surface area of the agent, pore size measurement Range
The specific surface area is more than or equal to 0.01m 2 (ii) in terms of/g. The average pore diameter of example 1 was 39.2nm and the pore distribution of the catalyst is shown in FIG. 1. The specific surface area is 2.3m 2 /g。
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.2 hours －1 The activity was evaluated at a reaction temperature of 590 ℃ and a water/ethylbenzene weight ratio of 1.6, and the test results are shown in Table 2.
Comparative example 1
Except that MgFe is not used 2 O 4 And MnO 2 Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions and the analysis method were the same as in example 1, specifically:
will correspond to 59.58 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 20.18 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.78 parts of K 2 Potassium carbonate of O, corresponding to 10.25 parts of CeO 2 Cerium oxalate of (1), corresponding to 2.71 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.5 parts of CaO and 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, extruded strips are taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven, dried at 90 ℃ for 2 hours and 160 ℃ for 3 hours, then the particles are put into a muffle furnace and calcined at 750 ℃ for 3 hours and 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
Comparative example 2
Except that red iron oxide, yellow iron oxide and MgO are used to replace MgFe in the same proportion 2 O 4 In addition, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, specifically:
will correspond to 58.59 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.84 parts of Fe 2 O 3 Iron oxide yellow of (1), equivalent to 4.55Portion K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Cerium oxalate equivalent to 2.58 parts of WO 3 Ammonium tungstate (D), calcium carbonate corresponding to 2.38 parts of CaO, 0.63 part of MgO, and 1.68 parts of MnO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
[ example 2]
In addition to using ZrO 2 Substitution for MnO 2 Except for the catalyst preparation method, the catalyst evaluation conditions and the analysis method, which are the same as those in example 1, specifically:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Cerium oxalate equivalent to 2.58 parts of WO 3 Ammonium tungstate (D), calcium carbonate equivalent to 2.38 parts of CaO, 3.16 parts of MgFe 2 O 4 1.68 parts of ZrO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
Comparative example 3
Except that red iron oxide, yellow iron oxide and MgO are used to replace MgFe in the same proportion 2 O 4 In addition, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, specifically:
will correspond to 58.59 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.84 parts of Fe 2 O 3 Corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate (D), calcium carbonate corresponding to 2.38 parts of CaO, 0.63 part of MgO, and 1.68 parts of ZrO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
[ example 3]
Except using TiO 2 Substitution for MnO 2 Except for the catalyst preparation method, the catalyst evaluation conditions and the analysis method, which are the same as those in example 1, specifically:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 1.68 parts of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
Comparative example 4
Except that red iron oxide, yellow iron oxide and MgO are used to replace MgFe in the same proportion 2 O 4 In addition, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions and the analysis method were the same as in example 1, specifically:
will correspond to 58.59 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 19.84 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Cerium oxalate equivalent to 2.58 parts of WO 3 Ammonium tungstate (D), calcium carbonate corresponding to 2.38 parts of CaO, 0.63 part of MgO, and 1.68 parts of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1. 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 part of MnO was used 2 And 0.84 part of ZrO 2 Substituted for 1.68 parts MnO 2 The method specifically comprises the following steps:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 0.84 part of MnO 2 0.84 part of ZrO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
[ example 5]
The catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 part MnO was used 2 And 0.84 part of TiO 2 Substituted for 1.68 parts MnO 2 The method specifically comprises the following steps:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 9.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 0.84 part of MnO 2 0.84 portion of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. 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 part of ZrO was used 2 And 0.84 part of TiO 2 Substituted for 1.68 parts MnO 2 The method specifically comprises the following steps:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 7.55 parts of K 2 Potassium carbonate of O, corresponding to 7.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 1.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 0.84 part of ZrO 2 0.84 part of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. 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 part of MnO was used 2 0.56 part of ZrO 2 And 0.56 part of TiO 2 Substituted for 1.68 parts MnO 2 The method specifically comprises the following steps:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 7.55 parts of K 2 Potassium carbonate of O, corresponding to 7.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 1.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 0.56 part of MnO 2 0.56 part of ZrO 2 0.56 part of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results are shown in Table 2.
[ example 8]
Will correspond to 53.88 parts of Fe 2 O 3 Iron oxide red of (1), corresponding to 17.05 parts of Fe 2 O 3 Iron oxide yellow of (2.35 parts by weight of K) 2 Potassium carbonate of O, corresponding to 11.9 parts of CeO 2 Corresponding to 4.16 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 3.35 parts of CaO, and 5.5 parts of MgFe 2 O 4 0.85 part of MnO 2 0.96 part of Nb 2 O 5 And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 9]
Equivalent to 52.73 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 13.45 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.55 parts of K 2 Potassium carbonate of O, corresponding to 10.55 parts of CeO 2 Cerium oxalate of (1.72 parts of WO) 3 Ammonium tungstate (D), calcium carbonate corresponding to 4.95 parts of CaO, and 7.65 parts of MgFe 2 O 4 And 4.4 parts of MnO 2 And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the mixture is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 10]
Equivalent to 55.36 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 17.42 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 3.71 parts of K 2 Potassium carbonate of O, corresponding to 9.46 parts of CeO 2 Cerium oxalate equivalent to 4.82 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 1.83 parts of CaO, 2.82 parts of MgFe 2 O 4 And 4.58 parts of MnO 2 And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 11]
Will correspond to 60.69 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 17.36 parts of Fe 2 O 3 Iron oxide yellow of (2), equivalent to 5.05 parts of K 2 Potassium carbonate of O, corresponding to 6.15 parts of CeO 2 Cerium oxalate equivalent to 2.03 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 0.55 part of CaO, and 6.15 parts of MgFe 2 O 4 2.02 parts of MnO 2 And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 5
Will correspond to 56.7 parts of Fe 2 O 3 Iron oxide red of (1), corresponding to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 7.55 parts of K 2 Potassium carbonate of O, corresponding to 7.75 parts of CeO 2 Corresponding to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 1.38 parts of CaO, and 3.16 parts of MgFe 2 O 4 1.68 parts of MnO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 3 hours at 750 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 6
Will correspond to 42.9 parts Fe 2 O 3 Iron oxide red of (5), corresponding to 25.8 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.8 parts of K 2 Potassium carbonate of O, corresponding to 9.1 parts of CeO 2 Cerium oxalate equivalent to 2.5 parts of WO 3 Ammonium tungstate (D), calcium carbonate corresponding to 4.1 parts of CaO, 4.9 parts of MgFe 2 O 4 4.9 parts of MnO 2 And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added and stirred for 0.5 hour,taking out the extruded strips, extruding the extruded strips into particles with the diameter of 3 mm and the length of 6 mm, putting the particles into an oven, drying the particles for 2 hours at the temperature of 90 ℃, drying the particles for 3 hours at the temperature of 160 ℃, then putting the particles into a muffle furnace, roasting the particles for 3 hours at the temperature of 750 ℃, and roasting the particles for 3 hours at the temperature of 920 ℃ to obtain finished catalysts, wherein the compositions of the catalysts are listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 7
Will correspond to 53.88 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 17.05 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.85 parts of K 2 Potassium carbonate of O, 7.11 parts of CeO 2 Equivalent to 4.42 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 3.35 parts of CaO, and 3.5 parts of MgFe 2 O 4 3.85 parts of MnO 2 0.99 part of MoO 3 And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 8
Will correspond to 50.36 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 17.42 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.45 parts of K 2 Potassium carbonate of O, corresponding to 6.15 parts of CeO 2 Corresponding to 3.29 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 2.73 parts of CaO, and 8.62 parts of MgFe 2 O 4 4.88 parts of MnO 2 Stirring 2.1 parts of cement and 4.95 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 25 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out extruded strips, extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking at 90 ℃ for 2 hours and at 160 ℃ for 3 hours, then putting the particles into a muffle furnace, baking at 750 ℃ for 3 hours and baking at 920 ℃ for 3 hoursThe finished catalyst was obtained with the catalyst composition as listed in table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 12]
Will correspond to 47.7 parts of Fe 2 O 3 Iron oxide red of (1), equivalent to 20.4 parts of Fe 2 O 3 Iron oxide yellow of (2), equivalent to 5.35 parts of K 2 Potassium carbonate of O, corresponding to 11.74 parts of CeO 2 Corresponding to 0.91 part of WO 3 Ammonium tungstate (D), calcium carbonate corresponding to 4.85 parts of CaO, and 4.65 parts of MgFe 2 O 4 4.4 parts of ZrO 2 And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 13]
Will correspond to 50.7 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 25.2 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.05 parts of K 2 Potassium carbonate of O, corresponding to 11.25 parts of CeO 2 Cerium oxalate equivalent to 2.58 parts of WO 3 Ammonium tungstate, calcium carbonate corresponding to 1.38 parts of CaO, and 0.95 part of MgFe 2 O 4 2.89 parts of TiO 2 And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 90 ℃ and 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 750 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Table 1 (wait for)
TABLE 1 (continuation)
TABLE 2
The above examples illustrate the addition of magnesium ferrite and a compound selected from MnO to an Fe-K-Ce-W-Ca catalytic system 2 、ZrO 2 Or TiO 2 The catalyst has less pores and proper specific surface control, obviously improves the low-temperature activity and stability of the low-potassium catalyst, can obviously reduce the use temperature of the catalyst on an industrial device, has obvious energy-saving effect, is beneficial to cost reduction and efficiency improvement of a styrene device, and is a novel energy-saving catalyst worthy of recommendation.
Claims (9)
1. A method for producing an alkyl-alkenyl aromatic hydrocarbon comprises a step of obtaining an alkyl-alkenyl aromatic hydrocarbon by subjecting an alkyl-aromatic hydrocarbon as a raw material to a dehydrogenation reaction in the presence of an ultra-low potassium catalyst; wherein the reaction temperature is 580-600 ℃, and the liquid space velocity is 0.5-1.5 hours －1 The weight of water is 1.0-2.0, the pressure is-40 KPa-normal pressure, the ultra-low potassium catalyst comprises the following components by weight percent: (a) 66-79% of Fe 2 O 3 (ii) a (b) 2 to 6 percent of K 2 O; (c) 6 to 12 percent of CeO 2 (ii) a (d) 0.5 to 5 percent of WO 3 (ii) a (e) 0.5 to 5 percent of CaO; (f) 0.5-8% of MgFe 2 O 4 (ii) a (g) 0.5-5% MnO 2 、ZrO 2 And TiO 2 (ii) a The catalyst does not contain molybdenum oxide;
the average aperture of the ultra-low potassium catalyst is 37.8-45.4 nm, and the specific surface area is 1.8-2.4 m 2 /g。
2. The process for producing an alkalkenyl aromatic hydrocarbon according to claim 1, wherein MgFe is contained in the aromatic hydrocarbon 2 O 4 The content is 1-7%.
3. The process for producing an alkalkenyl aromatic hydrocarbon according to claim 2, wherein MgFe is used as the main component 2 O 4 The content is 2-6%.
4. A method for producing an alkanylarene according to any one of claims 1 to 3, wherein the catalyst is prepared by a method comprising the steps of: mixing Fe source, K source, ce source, W source, ca source and MgFe according to a certain proportion 2 O 4 、MnO 2 、ZrO 2 、TiO 2 Uniformly contacting with a pore-forming agent and water to obtain the catalyst; wherein, no binder is added in the preparation process of the catalyst, and the binder comprises kaolin, diatomite and cement.
5. The process for producing an alkalkenyl arene according to claim 4, wherein Fe 2 O 3 Is added in the form of iron oxide red and iron oxide yellow, and the proportion of the iron oxide red and the iron oxide yellow is Fe 2 O 3 ：Fe 2 O 3 ·H 2 O=（1.8～3.1）:1。
6. The method for producing an alkylalkenyl aromatic hydrocarbon according to claim 4, wherein the method for preparing the catalyst comprises the steps of extruding, drying and calcining.
7. The process for producing an alkylalkenyl aromatic hydrocarbon according to claim 6, wherein the drying is carried out by a two-step method at 80 to 120 ℃ and 130 to 160 ℃.
8. The process for producing an alkylalkenyl aromatic hydrocarbon according to claim 6, wherein the calcination temperature is 700 to 1000 ℃.
9. The process for producing an alkenylarene according to claim 4, wherein the Ce source is added in the form of cerium oxalate or cerium hydroxide.
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| CN112239392B (en) * | 2019-07-16 | 2023-08-29 | 中国石油化工股份有限公司 | Method for dehydrogenating alkyl arene at low temperature |
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| CN101623642A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio |
| CN103372452A (en) * | 2012-04-24 | 2013-10-30 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene through ethyl benzene dehydrogenation and preparation method thereof |
| CN106582693A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof |
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| WO1997018034A1 (en) * | 1995-11-15 | 1997-05-22 | China Petro-Chemical Corporation | A catalyst for manufacturing alkyl aromatics and production method and use thereof |
| CN101623642A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio |
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| CN106582693A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof |
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