CN114425359B - Dehydrogenation catalyst for preparing styrene, preparation method and application thereof and ethylbenzene dehydrogenation method - Google Patents
Dehydrogenation catalyst for preparing styrene, preparation method and application thereof and ethylbenzene dehydrogenation method Download PDFInfo
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- CN114425359B CN114425359B CN202011099431.XA CN202011099431A CN114425359B CN 114425359 B CN114425359 B CN 114425359B CN 202011099431 A CN202011099431 A CN 202011099431A CN 114425359 B CN114425359 B CN 114425359B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 90
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 94
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 38
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 34
- 235000011181 potassium carbonates Nutrition 0.000 claims description 34
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000395 magnesium oxide Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims description 18
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004113 Sepiolite 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
- 229960000892 attapulgite Drugs 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 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 2
- 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 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 3
- 239000003361 porogen Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 63
- 230000003197 catalytic effect Effects 0.000 abstract description 34
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 30
- 239000000203 mixture Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DIGZKZLYDYJFHH-UHFFFAOYSA-N [K].[Mo].[Ce].[Fe] Chemical compound [K].[Mo].[Ce].[Fe] DIGZKZLYDYJFHH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 alkyl arene Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- B01J23/70—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
- B01J23/002—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of catalyst preparation, and discloses a dehydrogenation catalyst for preparing styrene, a preparation method and application thereof, and an ethylbenzene dehydrogenation method, wherein the dehydrogenation catalyst contains 74-95 wt% of oxide of main catalytic element and 0.8-5 wt% of WO (WO) 3 0.7-5% by weight of MgO, 0.5-5% by weight of BaO, 0.5-7% by weight of Li 2 O and 0.5-5 wt% of oxide of V group metal element, wherein the main catalytic elements are Fe element, K element and Ce element; wherein the alkali amount of the catalyst is 0.387-0.455mmol/g. The catalyst has better catalytic selectivity and ethylbenzene conversion rate even under the condition of high mass airspeed, and has the advantages of low benzene content in the product, energy conservation and consumption reduction.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a dehydrogenation catalyst for preparing styrene, a preparation method and application thereof, and a method for ethylbenzene dehydrogenation by using the catalyst.
Background
The main reaction of ethylbenzene dehydrogenation isC 6 H 5 -C 2 H 5 →C 6 H 5 CH＝CH 2 +H 2 +124KJ/mol, toluene and benzene are major by-products. At present, the industrial alkyl arene dehydrogenating catalyst is mainly Fe-K-Ce-Mo series catalyst, such as ZL91109968.9 and ZL95113340.3, which have high activity and selectivity, but K in the component is used as a cocatalyst 2 The O content is quite high. For example, ZL91109968.9 is a dehydrogenation catalyst for alkylaromatics, which comprises an iron-potassium-cerium-molybdenum system and a plurality of metal oxides, and specifically comprises the following components in percentage by weight: fe (Fe) 2 O 4 40-70％，K 2 CO 3 10-40％，Ce 2 O 3 3-10％，MoO 3 0.5-5%, mgO0.05-5%, and 0.001-5% of at least one oxide selected from Cu, zn, sc, ti, W, mn, ni, pd, al, P, bi, B, sn, pb, si; fe used in preparation of the catalyst 2 O 3 From Fe 2 O 3 And Fe (Fe) 2 O 3 ·H 2 O is composed of Fe 2 O 3 ∶Fe 2 O 3 ·H 2 The weight ratio of O is 0.2-5:1, the pore-forming agent is 1-2%, and the rest is adhesive. The catalyst has higher conversion rate and selectivity, but the component K in the catalyst 2 The O content is up to about 30%, and due to the strong water absorption of potassium, the potassium gradually migrates to the inside of particles in the dehydrogenation reaction process or is easy to wash, so that the stability of the catalyst is reduced, and the service life of the catalyst is influenced.
The byproduct is an important index for checking the performance of the catalyst, and under the same condition, the styrene device preferably selects the catalyst with few byproducts and good styrene selectivity. As CN1173781C, a dehydrogenation catalyst for steam-containing alkylaromatic feed streams is disclosed, comprising a catalyst as described in Fe 2 O 3 30 to 90 weight percent iron compound, 1 to 50 weight percent alkali metal source calculated as alkali metal oxide, and 0.1 to 1000ppm of a noble metal source selected from noble metal elements, noble metal-containing compounds, and combinations thereof, wherein all weight percentages are based on the total weight of the catalyst. The catalyst is usedThe catalyst has high selectivity and less byproducts, but noble metals are used in the catalyst, so that the catalyst has high cost and is difficult to realize industrial application.
In addition, in order to exploit the potential of the styrene plant to obtain as much styrene product as possible, to reduce production costs, to maximize benefits, higher demands are placed on the ability of ethylbenzene dehydrogenation catalysts to withstand high space velocities. The development of the catalyst is suitable for high space velocity, obtains as many styrene products as possible, simultaneously reduces unit consumption and energy consumption, reduces the content of byproduct benzene, realizes the maximization of benefits, and becomes urgent need of many styrene devices, especially large-scale styrene devices, at home and abroad.
Disclosure of Invention
The invention aims to solve the problems of low styrene selectivity, low ethylbenzene conversion rate, high byproduct content and intolerance to high airspeed of a conventional catalyst when the catalyst in the prior art adopts noble metal or does not adopt noble metal, and provides a dehydrogenation catalyst for preparing styrene, a preparation method and application thereof, and an ethylbenzene dehydrogenation method.
In order to achieve the above object, the present invention provides, in one aspect, a dehydrogenation catalyst for producing styrene comprising 74 to 95% by weight of an oxide of a main catalyst element, 0.8 to 5% by weight of WO, based on the total amount of the dehydrogenation catalyst 3 0.7-5% by weight of MgO, 0.5-5% by weight of BaO, 0.5-7% by weight of Li 2 O and 0.5-5 wt% of oxide of V group metal element, wherein the main catalytic elements are Fe element, K element and Ce element; wherein the alkali amount of the catalyst is 0.387-0.455mmol/g.
A second aspect of the present invention provides a method for producing a dehydrogenation catalyst for producing styrene according to the first aspect, comprising: mixing Fe source, K source, ce source, W source, mg source, ba source, li source, V group metal element source, pore-forming agent, solvent and selectively added B source, optionally drying, and roasting.
In a third aspect, the present invention provides a dehydrogenation catalyst for preparing styrene prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides the use of a dehydrogenation catalyst for the preparation of styrene according to the first or third aspect in ethylbenzene dehydrogenation.
In a fifth aspect, the present invention provides a process for the dehydrogenation of ethylbenzene comprising: ethylbenzene is subjected to dehydrogenation by contacting with the dehydrogenation catalyst according to the first or third aspect.
The prior art does not require the alkali amount of the catalyst for ethylbenzene dehydrogenation, and the total alkali amount is generally less than 3.2 mmol/g. The inventors of the present invention have found through studies that the ethylbenzene dehydrogenation catalyst contains a specific content of oxides of main catalytic elements (Fe element, K element and Ce element), WO 3 、MgO、BaO、Li 2 The catalyst has better catalytic selectivity and ethylbenzene conversion rate under the condition that the alkali content of the catalyst is 0.387-0.455mmol/g, and the benzene content in the product is lower, and the catalyst has better catalytic effect than the conventional catalyst under the condition of low space velocity even under the condition of high mass space velocity, so the catalyst has great advantages in the aspects of catalytic performance and energy conservation and consumption reduction.
Drawings
FIG. 1 is CO of the catalyst in example 1 of the present invention 2 -a profile of TPD.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a dehydrogenation catalyst for preparing styrene, which comprises 74 to 95 weight percent of an oxide of a main catalyst element and 0.8 to 5 weight percent of WO, based on the total amount of the dehydrogenation catalyst 3 0.7-5% by weight of MgO, 0.5-5% by weight of BaO, 0.5-7% by weight of Li 2 O and 0.5-5 wt% of oxide of V group metal element, wherein the main catalytic elements are Fe element, K element and Ce element; wherein the alkali amount of the catalyst is 0.387-0.455mmol/g.
According to the invention, the amount of base of the catalyst is between 0.395 and 0.440mmol/g; preferably 0.397 to 0.431mmol/g. In a preferred embodiment, the catalyst of the invention has better performance in terms of catalytic selectivity and ethylbenzene conversion, and the benzene content in the product is lower, so that the catalytic advantage is more obvious under the condition of high mass space velocity.
According to the invention, the catalyst has a base content of 0.387 to 0.455mmol/g, preferably 0.395 to 0.440mmol/g; more preferably 0.397 to 0.431mmol/g, and may be, for example, 0.397mmol/g,0.4mmol/g,0.405mmol/g,0.410mmol/g,0.415mmol/g,0.420mmol/g,0.425mmol/g,0.428mmol/g,0.431mmol/g, and any value between any two values.
The alkali content of the catalyst is analyzed by adopting a carbon dioxide-programmed temperature rising desorption method, 0.1g of the catalyst is activated in He airflow at 600 ℃ for 2 hours during analysis, then the temperature is reduced to 80 ℃ and CO is adsorbed 2 To equilibrium, purge with He gas to remove physically adsorbed CO 2 Then the temperature is programmed to rise from 80 ℃ to 600 ℃ at 10 ℃/min, and the CO is recorded 2 -TPD profile with CO desorbed collected with liquid nitrogen 2 Collecting the obtained CO 2 Quantitative analysis was performed by gas chromatography. Typical CO 2 The TPD map is shown in figure 1, the peak in the low temperature region is the desorption peak corresponding to the weak base amount, and the peak in the high temperature region is the desorption peak corresponding to the strong base amount, and the CO is recorded 2 -CO desorbed with liquid nitrogen while TPD profile is collected 2 Quantitatively analyzing the collected CO by gas chromatography 2 Content, calculate the correspondingThe alkali amount is the sum of the alkali amount and the alkali amount.
According to the invention, the main catalyst elements are Fe element, K element and Ce element, wherein the oxide content of the Fe element, the K element and the Ce element can be adjusted in a wider range, such as K 2 The content of O can be higher than 12 wt% by using a conventional catalyst, so long as the alkali content is 0.387-0.455mmol/g in the invention, and the catalyst has better selectivity and ethylbenzene conversion rate in cooperation with the other components, can meet the requirement of high-quality airspeed, and has lower benzene content in the obtained product. Preferably, K 2 The content of O is not more than 12% by weight.
In a preferred embodiment of the present invention, the dehydrogenation catalyst preferably comprises from 65 to 79 wt% of Fe, based on the total amount of the dehydrogenation catalyst 2 O 3 2-6 wt% of K 2 O,7-10 wt% CeO 2 WO 0.8-5 wt% 3 0.7-5% by weight of MgO, 0.5-5% by weight of BaO, 0.5-7% by weight of Li 2 O and 0.5 to 5 wt.% of an oxide of a group v metal element. In this case, K in the catalyst 2 O is only 2-6 wt%, which is significantly lower than the prior art, and K is 12 wt% or more 2 O catalyst such that the catalyst of the invention is specific for K 2 The dependency of O is reduced, the catalytic stability is stronger, and further, in the preferred embodiment, the catalyst of the invention also has higher catalytic selectivity and ethylbenzene conversion rate under the condition of high mass space velocity, and the benzene content in the product is also lower, so that the catalyst has lower material consumption and energy consumption.
In a more preferred embodiment of the present invention, in order to further increase the selectivity of the catalyst and the ethylbenzene conversion, the benzene content of the product is reduced, preferably the dehydrogenation catalyst contains 65.5 to 74 wt% of Fe based on the total amount of the dehydrogenation catalyst 2 O 3 3-5.5 wt% of K 2 O,7.5-9.5 wt% CeO 2 WO 1.5-4 wt% 3 1.5-3.5% by weight MgO, 1.5-4% by weight BaO,1-6 wt% Li 2 O and 1-4 wt% of an oxide of a group V metal element.
According to the present invention, preferably, fe in the dehydrogenation catalyst 2 O 3 The content of (c) is 65.5-74 wt%, and may be, for example, 65.5 wt%, 66 wt%, 66.5 wt%, 67 wt%, 67.5 wt%, 68 wt%, 68.5 wt%, 69 wt%, 69.5.5 wt%, 70 wt%, 70.5 wt%, 71 wt%, 71.5 wt%, 72 wt%, 72.5 wt%, 73 wt%, 73.5 wt%, 74 wt%, and any value between any values.
According to the invention, preferably, K in the dehydrogenation catalyst 2 The content of O is 3 to 5.5 wt%, for example, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%.
According to the present invention, preferably, ceO in the dehydrogenation catalyst 2 The content of (c) is 7.5-9.5 wt%, and may be, for example, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, and any value between any values.
According to the invention, preferably, WO in the dehydrogenation catalyst 3 The content of (c) is 1.5-4 wt%, and may be, for example, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value between any values.
According to the invention, preferably, the content of MgO in the dehydrogenation catalyst is between 1.5 and 3.5 wt.%, and may be, for example, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, and any value in between.
According to the invention, the content of BaO in the dehydrogenation catalyst is preferably 1.5-4 wt%, and may be, for example, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value between any values.
According to the present invention, preferably, li in the dehydrogenation catalyst 2 The O content is 1-6 wt%, for example, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%Percent, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, and any value between any number.
According to the present invention, the content of the group v metal element oxide in the dehydrogenation catalyst is preferably 1 to 4 wt%, and may be, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value between any values.
According to the present invention, the group v metal element oxide may be a group vb metal element oxide and/or a group va metal element oxide; the VB metal element may be, for example, nb and/or V, the VA metal may be, for example, sb and/or Bi, preferably the VB metal element is at least one of Sb, nb and V, i.e., the oxide of the V metal element is preferably Sb 2 O 5 、Nb 2 O 5 And V 2 O 5 At least one of them.
In order to further improve the selectivity of the catalyst and the ethylbenzene conversion and reduce the benzene content in the product, it is preferable that the group V metal element oxide is Sb 2 O 5 、Nb 2 O 5 And V 2 O 5 At least two of them. For example, it may be Sb 2 O 5 And Nb (Nb) 2 O 5 ；Nb 2 O 5 And V 2 O 5 ；V 2 O 5 And Sb (Sb) 2 O 5 ；Sb 2 O 5 、V 2 O 5 And Nb (Nb) 2 O 5 It is understood that in this case, the content of each group v metal element oxide may be the same or different. Further preferably, the group V metal element oxide is Sb 2 O 5 、Nb 2 O 5 And V 2 O 5 . The contents of the three can be adjusted within a wide range, the invention is not particularly limited, and in a more preferable embodiment of the invention, sb in the catalyst 2 O 5 、Nb 2 O 5 And V 2 O 5 The mass ratio of (2) is 1:0.8-1.2:0.8-1.2.
In a preferred embodiment of the present invention,the dehydrogenation catalyst also contains B 2 O 3 Preferably B 2 O 3 The content of (C) is 0.05 to 0.5% by weight, more preferably 0.2 to 0.4% by weight. In this embodiment, the catalyst has higher selectivity and ethylbenzene conversion, and lower benzene content in the product, even at high mass space velocities.
According to the invention, the catalyst can adopt the element types and the proportion, and can be added with other auxiliary agents, for example, can also contain TiO 2 The present invention can be realized. Preferably, the TiO in the catalyst 2 Is 0.3 to 1.5 wt.%, more preferably TiO 2 The content of (C) is 0.5-1 wt%.
In a preferred embodiment of the invention, the catalyst does not contain molybdenum oxide.
In a preferred embodiment of the invention, the catalyst does not contain a binder; without binder, the catalyst shows better catalytic selectivity and ethylbenzene conversion, and the benzene content in the product is lower. Preferably, the binder is at least one selected from the group consisting of cement, attapulgite, waterslide, stone bentonite, kaolin, montmorillonite, halloysite, diatomaceous earth, saponite, rectorite, quasi halloysite and sepiolite.
A second aspect of the present invention provides a method for producing a dehydrogenation catalyst for producing styrene according to the first aspect, comprising: mixing the pore-forming agent and the solvent with a Fe source, a K source, a Ce source, a W source, a Mg source, a Ba source, a Li source, a V group metal element source and a selectively added B source, and then sequentially drying and roasting.
The specific mode of the mixing can be selected in a wider range, so long as the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the V group metal element source, the pore-forming agent, the solvent and the selectively added B source can be uniformly mixed. Preferably in a kneader.
In a preferred embodiment of the invention, the K source is added in two parts, preferably in a manner comprising: firstly, carrying out first mixing on a Fe source, a first part of K source, a Ce source, a W source, a Mg source, a Ba source, a Li source, a V group metal element source, a pore-forming agent and a selectively added B source, then adding a second part of K source for second mixing, and finally adding a solvent for third mixing; with the preferred embodiment, the components are uniformly mixed, so that the catalytic selectivity and the ethylbenzene conversion rate can be further improved, and the benzene content in the product is lower.
The addition amount of the first part K source and the second part K source can be adjusted in a wider range, preferably K 2 O is calculated, and the mass ratio of the first part K source to the second part K source is 1.2-2:1; in the preferred embodiment, the K source is distributed more uniformly, the catalytic selectivity and the ethylbenzene conversion rate can be further improved, and the benzene content in the product is lower.
According to the invention, the mass ratio of the first part K source to the second part K source is preferably 1.2-2:1, and may be, for example, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, or any value between any two values.
The time of the first mixing, the second mixing and the third mixing is not particularly limited as long as the materials are uniformly mixed in the above-mentioned material addition sequence. Preferably, the time of the first mixing, the time of the second mixing and the time of the third mixing are each independently 0.4 to 1.5h; further preferably, the first mixing time is 0.4 to 1h, the second mixing time is 0.5 to 1.5h, and the third mixing time is 0.5 to 1.5h.
According to the present invention, the addition amount of the pore-forming agent may be adjusted within a wide range, and in order to make the catalyst have a high specific surface agent and a high strength, it is preferable that the addition amount of the pore-forming agent is 2.2 to 6.3 wt%, preferably 2 to 6 wt%, of the total addition amount of the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the v group metal element source and the selectively added B source, and the addition amounts of the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the v group metal element source and the selectively added B source are all calculated as oxides.
The pore-forming agent may be selected from pore-forming agents conventional in the art, preferably, the pore-forming agent is selected from at least one of graphite, polystyrene, and cellulose and derivatives thereof.
The addition amount of the solvent may be adjusted in a wide range so long as the material is kneaded and molded, and preferably the addition amount of the solvent is 17 to 33% by weight of the total addition amount of the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the v group metal element source and the selectively added B source, and the addition amounts of the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the v group metal element source and the selectively added B source are all calculated as oxides.
For the selection of the solvent, a solvent which is conventional in the art may be used as long as the above-mentioned mixing requirements can be satisfied. Preferably, the solvent is water.
In a preferred embodiment of the invention, the method further comprises shaping the mixed material prior to said drying.
The shape of the catalyst is not particularly limited, and may be, for example, granular, bar-shaped, etc., and in a preferred embodiment of the present invention, the method further comprises molding the mixed material before the drying. Those skilled in the art can shape the materials into various usable specifications according to the specific requirements in actual production. The embodiment of the present invention is exemplified by extruding particles 3 mm in diameter and 6 mm in length, and the present invention is not limited thereto.
In the above technical scheme, the drying conditions can be adjusted within a wide range, as long as the conventional roasting conditions are satisfied after drying. Preferably, the drying conditions include: the temperature is 35-135 ℃ and the time is 0.55-8h; more preferably, the drying conditions include: drying at 35-70deg.C for 2-4 hr, and heating to 80-135deg.C for 0.5-4 hr.
The conditions for calcination may be adjusted within a wide range as long as each metal source in the catalyst is converted into an oxide of the corresponding element after calcination, and the present invention can be realized. Preferably, the roasting conditions include: the temperature is 350-850 ℃ and the time is 2-8h; further preferably, the conditions of the firing include: roasting for 2-4h at 350-600 ℃, and then heating to 700-850 ℃ for roasting for 2-4h.
The Mg source is not particularly limited, and may be any magnesium-containing compound that can be converted into MgO in a subsequent firing process. Preferably, the Mg source is at least one of magnesium carbonate, magnesium oxide and magnesium hydroxide.
The present invention is not particularly limited as to the Ba source, and may be any barium-containing compound capable of being converted into BaO in the subsequent firing process, and preferably, the Ba source is at least one of barium carbonate, barium oxide, and barium hydroxide.
The Fe source is not particularly limited, and may be any one that can be converted into Fe in the subsequent firing process 2 O 3 Preferably, the Fe source is iron oxide red and/or iron oxide yellow, more preferably iron oxide red and iron oxide yellow. In the case that the Fe source is iron oxide red and iron oxide yellow, the addition ratio of the two materials can be adjusted in a wider range, and further preferably, the weight ratio of the iron oxide red to the iron oxide yellow is (2.6-3.9) in terms of oxide: 1.
The Ce source is not particularly limited, and may be any source capable of being converted into CeO in the subsequent firing process 2 Preferably, the Ce source is cerium acetate and/or cerium carbonate.
The K source is not particularly limited, and may be any source capable of being converted into K in the subsequent firing process 2 The potassium-containing compound of O, e.g., potassium carbonate, potassium bicarbonate, potassium hydroxide, etc., preferably, the K source is potassium carbonate and/or potassium bicarbonate. In the present invention, the types of the first partial K source and the second partial K source may be the same or different, and the present invention is not limited thereto.
The W source is not particularly limited, and may be any one that can be converted into WO in the subsequent firing process 3 Preferably, the W source is selected from at least one of ammonium tungstate, ammonium metatungstate, and tungsten trioxide.
For B source, the inventionThere is no particular limitation, and can be any that can be converted to B in a subsequent firing process 2 O 3 Boron-containing compounds of (B), e.g. B 2 O 3 Salts containing borates, and the like, preferably, the B source is B 2 O 3 。
The source of the group V metal element is not particularly limited, and may be, for example, a salt and/or an oxide containing the group V metal element. The selection of the metal element is the same as that described above, and will not be described again here.
In a third aspect, the present invention provides a dehydrogenation catalyst for preparing styrene prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides the use of a dehydrogenation catalyst for the preparation of styrene according to the first or third aspect in ethylbenzene dehydrogenation. The catalyst of the invention has stronger catalytic selectivity and ethylbenzene conversion rate in ethylbenzene dehydrogenation, and the benzene content in the product is lower, and even under the condition of high mass space velocity, compared with the conventional catalyst, the catalyst still exceeds the conventional catalyst in the aspects of catalytic selectivity, ethylbenzene conversion rate and low benzene byproduct.
In a fifth aspect, the present invention provides a process for the dehydrogenation of ethylbenzene comprising: ethylbenzene is subjected to dehydrogenation by contacting with the dehydrogenation catalyst according to the first or third aspect.
According to the present invention, the dehydrogenation conditions for ethylbenzene can be adjusted within a wide range, and preferably, the dehydrogenation reaction conditions include: the mass airspeed is 1.2-1.8h -1 The temperature is 600-650 ℃, the weight ratio of water to ethylbenzene is 1.0-2.0, and the pressure is-60 kPa to normal pressure. Under the condition, the ethylbenzene dehydrogenation method has strong catalytic selectivity and ethylbenzene conversion rate, and the benzene content in the product is low. Due to the conventional mass space velocity of 0.7h -1 The catalyst provided by the invention can be suitable for higher space velocity (for example, 1.2-1.8h -1 ) Therefore, the ethylbenzene dehydrogenation method has obvious advantages in the aspects of energy conservation and consumption reduction.
To ensure higher catalytic selectivity and ethylbenzene conversionIn the case of low benzene by-product, the energy consumption is further reduced, and further preferably, the dehydrogenation reaction conditions include: the mass airspeed is 1.4-1.7h -1 The temperature is 600-630 ℃, the weight ratio of water to ethylbenzene is 1.2-1.6, and the pressure is-40 kPa to-20 kPa.
According to the present invention, the ethylbenzene dehydrogenation temperature is preferably 600 to 630℃and may be, for example, 600℃605℃610℃615℃620℃625℃630℃or any value between any two values.
According to the invention, the mass space velocity is preferably from 1.4 to 1.7h -1 For example, it may be 1.4h -1 、1.5h -1 、h -1 、1.6h -1 、1.7h -1 And any value between any two values.
According to the invention, the weight ratio of water to ethylbenzene (water ratio) is preferably 1.2-1.6, and may be, for example, 1.2, 1.3, 1.4, 1.5, 1.6, and any value between any two values.
According to the present invention, the pressure is preferably from-40 kPa to-20 kPa, and may be, for example, from-40 kPa, -35kPa, -30kPa, -25kPa, -20kPa, and any value between any two values.
In the invention, the performance of the catalyst is respectively characterized by ethylbenzene conversion rate, styrene selectivity and benzene mass content in the product, and the catalyst is specifically subjected to performance evaluation in an isothermal fixed bed, wherein 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 filled with 100 ml of catalyst in a stainless steel tube having an inner diameter of 1 inch. The reaction product flowing out of the reactor was condensed and analyzed for ethylbenzene concentration (wt.%), styrene concentration (wt.%), benzene concentration (wt.%) and toluene concentration (wt.%), by a gas chromatograph;
ethylbenzene conversion% = (initial ethylbenzene concentration in reaction mass (wt%) -ethylbenzene concentration in reaction product (wt%));
styrene selectivity% = styrene concentration in reaction product (wt%)/(initial ethylbenzene concentration in reaction mass (wt%) -ethylbenzene concentration in reaction product (wt%));
the alkali content of the catalyst is analyzed by adopting a carbon dioxide-programmed temperature rising desorption method, 0.1g of the catalyst is activated in He airflow at 600 ℃ for 2 hours during analysis, then the temperature is reduced to 80 ℃ and CO is adsorbed 2 To equilibrium, purge with He gas to remove physically adsorbed CO 2 Then the temperature is programmed to rise from 80 ℃ to 600 ℃ at 10 ℃/min, and the CO is recorded 2 -TPD profile with CO desorbed collected with liquid nitrogen 2 Collecting the obtained CO 2 Quantitative analysis was performed by gas chromatography. Typical CO 2 The TPD map is shown in figure 1, the peak in the low temperature region is the desorption peak corresponding to the weak base amount, and the peak in the high temperature region is the desorption peak corresponding to the strong base amount, and the CO is recorded 2 -CO desorbed with liquid nitrogen while TPD profile is collected 2 Quantitatively analyzing the collected CO by gas chromatography 2 And calculating the corresponding weak alkali amount and strong alkali amount, wherein the total alkali amount is the sum of the weak alkali amount and the strong alkali amount.
The present invention will be described in detail by examples. In the following examples, iron oxide red, iron oxide yellow and graphite are commercially available products meeting the national standard requirements.
Example 1
Based on oxide, corresponds to 57.16 parts by weight of Fe 2 O 3 Iron oxide red of (2) and equivalent to 14.67 parts by weight of Fe 2 O 3 Iron oxide yellow of (3.36 parts by weight of K) 2 Potassium carbonate of O, equivalent to 8.76 parts by weight of CeO 2 Cerium acetate equivalent to 2.76 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.3 parts by weight of MgO, barium carbonate corresponding to 3.7 parts by weight of BaO, 2.86 parts by weight of Li 2 O, 1.32 parts by weight of Sb 2 O 5 0.3 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with a K equivalent to 1.81 parts by weight being added 2 O potassium carbonate, stirring for 0.8 hr, adding catalyst element source (iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, magnesium hydroxide, barium carbonate, li) calculated as oxide 2 O、Sb 2 O 5 And B 2 O 3 ) Deionized water accounting for 23.9 percent of the total weight is mixed for 0.8 hour, extruded strips are taken out, extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, put into an oven, baked for 2.5 hours at 65 ℃ and 3.0 hours at 125 ℃, then put into a muffle furnace, baked for 3 hours at 550 ℃ and baked for 3 hours at 740 ℃ to obtain the finished catalyst, and the catalyst composition is shown in table 1.
The amount of alkali in the catalyst was analyzed by a carbon dioxide-temperature programmed desorption method, and the results are shown in Table 3.
100 ml of catalyst was charged into the reactor at-30 kPa, mass space velocity of 1.5h －1 The performance was evaluated at 620℃and a weight ratio of water to ethylbenzene of 1.5, and the results of the evaluation are shown in Table 3 and Table 4, respectively, after 100 hours of reaction.
Comparative example 1
A dehydrogenation catalyst was prepared as in example 1, except that Li was not added 2 O and Sb 2 O 5 The evaluation conditions and analysis method were the same as in example 1, and specifically:
based on oxide, corresponds to 59.66 parts by weight of Fe 2 O 3 Iron oxide red of 15.31 parts by weight of Fe 2 O 3 Iron oxide yellow of (3.51 parts by weight of K) 2 Potassium carbonate of O, equivalent to 9.14 parts by weight of CeO 2 Cerium acetate equivalent to 2.88 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.44 parts by weight of MgO, barium carbonate corresponding to 3.86 parts by weight of BaO, 0.31 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with a K equivalent to 1.89 parts by weight being added 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 1. The evaluation results are shown in tables 3 and 4, respectively.
Comparative example 2
A dehydrogenation catalyst was prepared as in example 1, except that Li was not added 2 The evaluation conditions and analysis method of the O and the catalyst are the same as those of example 1, and specifically:
will correspond to 58.84 parts by weight of Fe 2 O 3 Iron oxide red of 15.1 parts by weight of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 3.46 parts by weight of K 2 Potassium carbonate of O, equivalent to 9.02 parts by weight of CeO 2 Cerium acetate equivalent to 2.84 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.4 parts by weight of MgO, barium carbonate corresponding to 3.81 parts by weight of BaO, 1.36 parts by weight of Sb 2 O 5 0.31 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with a K equivalent to 1.86 parts by weight being added 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 1. The evaluation results are shown in tables 3 and 4, respectively.
Example 2
A dehydrogenation catalyst was prepared as described in example 1, except that an equivalent amount of Nb was used 2 O 5 Replacement of Sb 2 O 5 The catalyst preparation method, evaluation conditions and analysis method were the same as in example 1, and the catalyst composition is shown in Table 1. The evaluation results are shown in tables 3 and 4, respectively.
Example 3
A dehydrogenation catalyst was prepared as described in example 1, except that an equivalent amount of V was used 2 O 5 Replacement of Sb 2 O 5 The catalyst preparation method, evaluation conditions and analysis method were the same as in example 1, and the catalyst composition is shown in Table 1. The evaluation results are shown in tables 3 and 4, respectively.
Example 4
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.66 parts by weight of Sb was used 2 O 5 And 0.66 part by weight of Nb 2 O 5 Replacement of 1.32 parts by weight of Sb 2 O 5 Catalyst groupThe results are shown in Table 1. The evaluation results are shown in tables 3 and 4, respectively.
Example 5
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.66 parts by weight of Sb was used 2 O 5 And 0.66 part by weight V 2 O 5 Replacement of 1.32 parts by weight of Sb 2 O 5 The catalyst composition is shown in Table 1, and the evaluation results are shown in tables 3 and 4, respectively.
Example 6
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.66 parts by weight of Nb was used 2 O 5 And 0.66 part by weight V 2 O 5 Replacement of 1.32 parts by weight of Sb 2 O 5 The catalyst composition is shown in Table 1, and the evaluation results are shown in tables 3 and 4, respectively.
Example 7
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.44 parts by weight of Sb was used 2 O 5 0.44 part by weight of Nb 2 O 5 And 0.44 part by weight V 2 O 5 Replacement of 1.32 parts by weight of Sb 2 O 5 The catalyst composition is shown in Table 1, and the evaluation results are shown in tables 3 and 4, respectively.
Example 8
Based on oxide, corresponds to 45.21 parts by weight of Fe 2 O 3 Iron oxide red of (2) and equivalent to 20.73 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.29 parts by weight of K) 2 Potassium carbonate of O, equivalent to 9.86 parts by weight of CeO 2 Cerium acetate equivalent to 4.47 parts by weight of WO 3 Magnesium hydroxide corresponding to 4.89 parts by weight of MgO, barium carbonate corresponding to 3.01 parts by weight of BaO, 3.56 parts by weight of Li 2 O, 3.86 parts by weight Nb 2 O 5 0.1 part by weight of B 2 O 3 0.78 part by weight of TiO 2 And 5.2 parts by weight of graphite were stirred in a kneader for 0.4h, with a K equivalent to 1.24 parts by weight being added 2 Potassium carbonate of O, equivalent to 9.86 parts by weight of CeO 2 Stirring for 1.5 hr, adding deionized water accounting for 23.9% of the total weight of the catalyst element source calculated as oxide, and mixingMixing for 0.5h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into a baking oven, baking at 70 ℃ for 2h, baking at 80 ℃ for 4h, then putting into a muffle furnace, baking at 350 ℃ for 4h, and baking at 700 ℃ for 4h to obtain the finished catalyst, wherein the catalyst composition is shown in table 1. The catalysts were prepared, evaluated, and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 9
Equivalent to 61.2 parts by weight of Fe in terms of oxide 2 O 3 Iron oxide red of (2) and equivalent to 13.93 parts by weight of Fe 2 O 3 Iron oxide yellow of 1.61 parts by weight K 2 Potassium carbonate of O, equivalent to 7.12 parts by weight of CeO 2 Cerium acetate equivalent to 0.83 parts by weight of WO 3 Magnesium hydroxide corresponding to 0.78 weight part of MgO, barium carbonate corresponding to 4.78 weight parts of BaO, and Li 4.88 weight parts 2 O, 3.55 parts by weight of Sb 2 O 5 0.45 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 1 hour, and K equivalent to 0.87 part by weight was added 2 O potassium carbonate, stirring for 0.5h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 1.5h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into a baking oven, baking at 70 ℃ for 2h and 135 ℃ for 0.5h, putting into a muffle furnace, baking at 600 ℃ for 2h and baking at 850 ℃ for 2h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 10
Based on oxide, corresponds to 62.44 parts by weight of Fe 2 O 3 Iron oxide red of 15.69 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.87 parts by weight of K) 2 Potassium carbonate of O, equivalent to 7.53 parts by weight of CeO 2 Cerium acetate equivalent to 4.57 parts by weight of WO 3 Magnesium hydroxide corresponding to 2.65 parts by weight of MgO, barium carbonate corresponding to 0.75 parts by weight of BaO, and 0.82 parts by weight of Li 2 O, 0.88 part by weight of Sb 2 O 5 0.25 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5 parth, adding 1.55 parts by weight of K 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 11
The content of Fe in the oxide is 55.49 parts by weight 2 O 3 Iron oxide red of (2) corresponding to 17.21 parts by weight of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 3.8 parts by weight of K 2 Potassium carbonate of O, equivalent to 8.64 parts by weight of CeO 2 Cerium acetate equivalent to 1.65 parts by weight of WO 3 Magnesium hydroxide corresponding to 2.85 parts by weight of MgO, barium carbonate corresponding to 2.8 parts by weight of BaO, 1.38 parts by weight of Li 2 O, 3.78 parts by weight of Sb 2 O 5 0.35 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with an addition of K corresponding to 2.05 parts by weight 2 Potassium carbonate of O, equivalent to 8.64 parts by weight of CeO 2 Adding deionized water accounting for 23.9 percent of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, drying at 65 ℃ for 2.5h and 125 ℃ for 3.0h, then putting into a muffle furnace, and roasting at 550 ℃ for 3h and 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 12
Based on oxide, corresponds to 51.36 parts by weight of Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.69 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.96 parts by weight of K) 2 Potassium carbonate of O, equivalent to 7.55 parts by weight of CeO 2 Cerium acetate equivalent to 3.5 parts by weight of WO 3 Corresponding to 1.41 parts by weight of MgOMagnesium hydroxide, barium carbonate corresponding to 1.95 parts by weight of BaO, 6.76 parts by weight of Li 2 O, 2.75 parts by weight of Sb 2 O 5 0.48 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with an addition of K corresponding to 1.59 parts by weight 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 13
Based on the oxide, will correspond to 50.1 parts by weight of Fe 2 O 3 Iron oxide red of 15.68 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.57 parts by weight of K) 2 Potassium carbonate of O, equivalent to 9.32 parts by weight of CeO 2 Cerium acetate equivalent to 4.88 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.85 parts by weight of MgO, barium carbonate corresponding to 3.89 parts by weight of BaO, 3.35 parts by weight of Li 2 O, 4.75 parts by weight of Sb 2 O 5 0.22 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, 1.39 parts by weight of K was added 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Example 14
A catalyst was prepared according to the procedure of example 1, except that potassium carbonate was added in one portion, specifically:
based on oxide, corresponds to 57.16 parts by weight of Fe 2 O 3 Iron oxide red of (2) and equivalent to 14.67 parts by weight of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 5.17 parts by weight of K 2 Potassium carbonate of O, equivalent to 8.76 parts by weight of CeO 2 Cerium acetate equivalent to 2.76 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.3 parts by weight of MgO, barium carbonate corresponding to 3.7 parts by weight of BaO, 2.86 parts by weight of Li 2 O, 1.32 parts by weight of Sb 2 O 5 0.3 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 1.3 hours, and a catalyst source (iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, magnesium hydroxide, barium carbonate, li) was added in an amount calculated as oxide 2 O、Sb 2 O 5 And B 2 O 3 ) Deionized water accounting for 23.9 percent of the total weight is mixed for 0.8 hour, extruded strips are taken out, extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, put into an oven, baked for 2.5 hours at 65 ℃ and 3.0 hours at 125 ℃, then put into a muffle furnace, baked for 3 hours at 550 ℃ and baked for 3 hours at 740 ℃ to obtain the finished catalyst, and the catalyst composition is shown in table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Comparative example 3
Based on oxide, corresponds to 46.52 parts by weight of Fe 2 O 3 Iron oxide red of (2) and equivalent to 23.1 parts by weight of Fe 2 O 3 Iron oxide yellow of (3.38 parts by weight of K) 2 Potassium carbonate of O, equivalent to 6.76 parts by weight of CeO 2 Cerium acetate equivalent to 2.76 parts by weight of WO 3 Magnesium hydroxide corresponding to 2.3 parts by weight of MgO, barium carbonate corresponding to 2.47 parts by weight of BaO, and 7.26 parts by weight of Li 2 O, 5.15 parts by weight of Sb 2 O 5 0.3 part by weight of B 2 O 3 And 5.2 parts by weight of graphite are stirred in a kneader for 2 hours, deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide is added, mixed for 0.8 hour, extruded into particles with the diameter of 3 mm and the length of 6 mm, put in an oven, baked for 2.5 hours at 65 ℃ and 3.0 hours at 125 ℃, then put in a muffle furnace, baked for 3 hours at 550 ℃ and baked for 3 hours at 740 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 2. Evaluation and analysis as in example 1The catalysts and results are shown in tables 3 and 4, respectively.
Comparative example 4
In terms of oxide, will correspond to 60.76 parts by weight Fe 2 O 3 Iron oxide red of (2) and equivalent to 15.19 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.85 parts by weight of K) 2 Potassium carbonate of O, equivalent to 8.76 parts by weight of CeO 2 Cerium acetate equivalent to 2.76 parts by weight of WO 3 Magnesium hydroxide corresponding to 2.9 parts by weight of MgO, barium carbonate corresponding to 3.7 parts by weight of BaO, 0.35 part by weight of Li 2 O, 0.45 part by weight of Sb 2 O 5 0.35 part by weight of B 2 O 3 Equivalent to 0.4 part by weight of MoO 3 The ammonium molybdate and 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, and 1.53 parts by weight of K was added thereto 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Comparative example 5
Equivalent to 60.84 parts by weight of Fe in terms of oxide 2 O 3 Iron oxide red of (2) and equivalent to 20.28 parts by weight of Fe 2 O 3 Iron oxide yellow of 1.22 parts by weight K 2 Potassium carbonate of O, equivalent to 7.15 parts by weight of CeO 2 Cerium acetate equivalent to 1.25 parts by weight of WO 3 Magnesium hydroxide corresponding to 1.35 parts by weight of MgO, barium carbonate corresponding to 2.77 parts by weight of BaO, 2.86 parts by weight of Li 2 O, 1.32 parts by weight of Sb 2 O 5 0.3 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with a K equivalent to 0.66 parts by weight being added 2 O potassium carbonate, stirring for 0.8 hr, adding deionized water accounting for 23.9% of the total weight of the catalyst element source calculated as oxide, mixing for 0.8 hr, taking out extruded strips, extruding into strips with diameter of 3 mm and length of 6 mmIs put into a baking oven, is baked for 2.5 hours at 65 ℃ and is baked for 3.0 hours at 125 ℃, is then put into a muffle furnace, is baked for 3 hours at 550 ℃ and is baked for 3 hours at 740 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Comparative example 6
The content of Fe in the oxide is 59.6 parts by weight 2 O 3 Iron oxide red of (2) and equivalent to 12.02 parts by weight of Fe 2 O 3 Iron oxide yellow of (2) and equivalent to 4.8 parts by weight of K 2 Potassium carbonate of O, 6.76 parts by weight of CeO 2 Equivalent to 2.76 parts by weight of WO 3 Magnesium hydroxide corresponding to 3.3 parts by weight of MgO, barium carbonate corresponding to 3.7 parts by weight of BaO, 2.86 parts by weight of Li 2 O, 1.32 parts by weight of Sb 2 O 5 0.3 part by weight of B 2 O 3 And 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with an addition of K corresponding to 2.58 parts by weight 2 O potassium carbonate, stirring for 0.8h, adding deionized water accounting for 23.9% of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into an oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in Table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
Comparative example 7
Based on the oxide, will correspond to 38.5 parts by weight of Fe 2 O 3 Iron oxide red of 40.63 parts by weight of Fe 2 O 3 Iron oxide yellow of (2.87 parts by weight of K) 2 Potassium carbonate of O, equivalent to 8.53 parts by weight of CeO 2 Cerium acetate equivalent to 3.66 parts by weight of WO 3 Magnesium hydroxide corresponding to 0.65 part by weight of MgO, barium carbonate corresponding to 0.75 part by weight of BaO, and Li corresponding to 0.82 part by weight 2 O, 0.8 part by weight of Sb 2 O 5 0.25 part by weight of B 2 O 3 0.99 part by weight of cement and 5.2 parts by weight of graphite were stirred in a kneader for 0.5h, with a K equivalent to 1.55 parts by weight being added 2 Potassium carbonate of O, againStirring for 0.8h, adding deionized water accounting for 23.9 percent of the total weight of the catalyst catalytic element source calculated by oxide, mixing for 0.8h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting into a baking oven, baking at 65 ℃ for 2.5h and 125 ℃ for 3.0h, putting into a muffle furnace, baking at 550 ℃ for 3h and baking at 740 ℃ for 3h to obtain the finished catalyst, wherein the catalyst composition is shown in table 2. The catalysts were evaluated and analyzed as in example 1, and the results are shown in tables 3 and 4, respectively.
TABLE 1
TABLE 2
TABLE 3 Table 3
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TABLE 4 Table 4
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Ethylbenzene dehydrogenation catalyst contains specific content of oxides of main catalytic elements (Fe element, K element and Ce element), WO 3 、MgO、BaO、Li 2 Under the condition that the alkali amount of the catalyst is 0.387-0.455mmol/g, the obtained catalyst shows better catalytic selectivity and ethylbenzene conversion rate, and the benzene content in the product is lower, and furthermore, the catalyst has better catalytic effect than the conventional catalyst under the condition of low space velocity even under the condition of high mass space velocity, and the catalyst is beneficial to cost reduction and efficiency increase of factories and is a dehydrogenation catalyst suitable for market demands.
According to detection, the activity evaluation is carried out on the isothermal fixed bed by using the catalyst of the invention, and the reaction is carried out at-30 kPa and ethylbenzene liquid space velocity of 1.5h －1 The reaction temperature is 620 ℃, the selectivity of the styrene reaches 96.53 percent under the condition of the water ratio (weight) of 1.5, the benzene content is as low as 0.33 percent, and the toluene content is as low as 2.36 percent, thus obtaining better technical effect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (43)
1. A dehydrogenation catalyst for preparing styrene, characterized in that the dehydrogenation catalyst contains 65-79 wt% of Fe based on the total amount of the dehydrogenation catalyst 2 O 3 2-6 wt% of K 2 O,7-10 wt% CeO 2 WO 0.8-5 wt% 3 0.7-5% by weight of MgO, 0.5-5% by weight of BaO, 0.5-7% by weight of Li 2 0.5 to 5 wt% of an oxide of a group V metal element;
wherein the alkali amount of the catalyst is 0.387-0.455mmol/g.
2. The dehydrogenation catalyst of claim 1, wherein the catalyst has a base amount of from 0.395 to 0.440mmol/g.
3. The dehydrogenation catalyst of claim 2, wherein the catalyst has a base amount of from 0.397 to 0.431mmol/g.
4. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst comprises from 65.5 to 74 weight percent Fe based on the total amount of the dehydrogenation catalyst 2 O 3 3-5.5 wt% of K 2 O,7.5-9.5 wt% CeO 2 WO 1.5-4 wt% 3 1.5 to 3.5 weight percent MgO,1.5 to 4 weight percent BaO,1 to 6 weight percent Li 2 O and 1-4 wt% of an oxide of a group V metal element.
5. The dehydrogenation catalyst of claim 1, further comprising B 2 O 3 。
6. The dehydrogenation catalyst of claim 5, wherein B 2 O 3 The content of (C) is 0.05-0.5 wt%.
7. The dehydrogenation catalyst of claim 6, wherein B 2 O 3 The content of (C) is 0.2-0.4 wt%.
8. The dehydrogenation catalyst of any of claims 1-7, wherein the group v metal element oxide is a group v metal element oxide and/or a group va metal element oxide.
9. The dehydrogenation catalyst of claim 8, wherein the group v metal element oxide is Sb 2 O 5 、Nb 2 O 5 And V 2 O 5 At least one of them.
10. The dehydrogenation catalyst of claim 9, wherein the group v metal element oxide is Sb 2 O 5 、Nb 2 O 5 And V 2 O 5 In (a) and (b)At least two kinds.
11. The dehydrogenation catalyst of any of claims 1-7, wherein the catalyst is free of molybdenum oxide.
12. The dehydrogenation catalyst of any of claims 1-7, wherein the catalyst does not comprise a binder.
13. The dehydrogenation catalyst of claim 12, wherein the binder is selected from at least one of cement, attapulgite, waterslide, stone bentonite, kaolin, montmorillonite, halloysite, diatomaceous earth, saponite, rectorite, quasi halloysite, and sepiolite.
14. The method for producing a dehydrogenation catalyst for producing styrene according to any one of claims 1 to 13, characterized by comprising: mixing the pore-forming agent and the solvent with a Fe source, a K source, a Ce source, a W source, a Mg source, a Ba source, a Li source, a V group metal element source and a selectively added B source, and then sequentially drying and roasting.
15. The method of claim 14, wherein the K source is added in two portions, the mixing comprising: firstly, carrying out first mixing on a Fe source, a first part of K source, a Ce source, a W source, a Mg source, a Ba source, a Li source, a V group metal element source, a pore-forming agent and a selectively added B source, then adding a second part of K source for second mixing, and finally adding a solvent for third mixing.
16. The method of claim 15, wherein the at least one of 2 O meter, the mass ratio of the first part K source to the second part K source is 1.2-2:1.
17. The method of claim 15, wherein the time of the first mixing, the time of the second mixing, and the time of the third mixing are each independently 0.4-1.5 hours.
18. The method of claim 17, wherein the first mixing is for 0.4-1h, the second mixing is for 0.5-1.5h, and the third mixing is for 0.5-1.5h.
19. The method according to any one of claims 14 to 18, wherein the pore-forming agent is added in an amount of 2.2 to 6.3% by weight based on the total addition amount of the Fe source, the K source, the Ce source, the W source, the Mg source, the Ba source, the Li source, the v-group metal element source, and the B source, which are selectively added, each calculated as an oxide.
20. The method of claim 19, wherein the porogen is added in an amount of 2-6 wt% of the total addition of the Fe source, K source, ce source, W source, mg source, ba source, li source, group v metal element source, and optionally B source.
21. The method of claim 19, wherein the pore-forming agent is selected from at least one of graphite, polystyrene, and cellulose and derivatives thereof.
22. The method according to any one of claims 14 to 18, wherein the solvent is added in an amount of 17 to 33% by weight of the total addition amount of the Fe source, K source, ce source, W source, mg source, ba source, li source, v group metal element source, and optionally B source, and the addition amounts of the Fe source, K source, ce source, W source, mg source, ba source, li source, v group metal element source, and optionally B source are all in terms of oxides.
23. The method of claim 22, wherein the solvent is water.
24. The method of any one of claims 14-18, further comprising shaping the mixed material prior to said drying.
25. The method of claim 24, wherein the drying conditions comprise: the temperature is 35-135 ℃ and the time is 0.55-8h.
26. The method of claim 25, wherein the drying conditions comprise: drying at 35-70deg.C for 2-4 hr, and heating to 80-135deg.C for 0.5-4 hr.
27. The method of claim 24, wherein the firing conditions include: the temperature is 350-850 ℃ and the time is 2-8h.
28. The method of claim 25, wherein the firing conditions include: roasting for 2-4h at 350-600 ℃, and then heating to 700-850 ℃ for roasting for 2-4h.
29. The method of any one of claims 14-18, wherein the Mg source is at least one of magnesium carbonate, magnesium oxide, and magnesium hydroxide.
30. The method of any one of claims 14-18, wherein the Ba source is at least one of barium carbonate, barium oxide, and barium hydroxide.
31. The method of any one of claims 14-18, wherein the Fe source is red iron oxide and/or yellow iron oxide.
32. The method of claim 31, wherein the Fe sources are red iron oxide and yellow iron oxide.
33. The method of claim 32, wherein the weight ratio of red iron oxide to yellow iron oxide, on an oxide basis, is (2.6-3.9): 1.
34. the method of any one of claims 14-18, wherein the Ce source is cerium acetate and/or cerium carbonate.
35. The method of any one of claims 14-18, wherein the K source is potassium carbonate and/or potassium bicarbonate.
36. The method of any one of claims 14-18, wherein the W source is selected from at least one of ammonium tungstate, ammonium metatungstate, and tungsten trioxide.
37. The method of any one of claims 14-18, wherein the B source is B 2 O 3 。
38. The method of any one of claims 14-18, wherein the source of group v metal element is a salt and/or oxide containing the group v metal element.
39. A dehydrogenation catalyst for the preparation of styrene prepared by the preparation method of any one of claims 14 to 38.
40. The use of a dehydrogenation catalyst according to any of claims 1-13 and 39 for the preparation of styrene in ethylbenzene dehydrogenation reactions.
41. A process for the dehydrogenation of ethylbenzene, comprising: contacting ethylbenzene with a dehydrogenation catalyst according to any one of claims 1-13 and 39 to effect dehydrogenation.
42. The ethylbenzene dehydrogenation process of claim 41 wherein the dehydrogenation reaction conditions comprise: the mass airspeed is 1.2-1.8h -1 The temperature is 600-650 ℃, the weight ratio of water to ethylbenzene is 1.0-2.0, and the pressure is-60 kPa to normal pressure.
43. The ethylbenzene dehydrogenation process according to claim 42 which comprisesThe dehydrogenation reaction conditions include: the mass airspeed is 1.4-1.7h -1 The temperature is 600-630 ℃, the weight ratio of water to ethylbenzene is 1.2-1.6, and the pressure is-40 kPa to-20 kPa.
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| CN1298856A (en) * | 2000-10-18 | 2001-06-13 | 中国石油天然气股份有限公司兰州石化分公司 | Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process |
| CN103028419A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for low-water ratio ethylbenzene dehydrogenation |
| CN105777480A (en) * | 2014-12-15 | 2016-07-20 | 中国石油天然气股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1298856A (en) * | 2000-10-18 | 2001-06-13 | 中国石油天然气股份有限公司兰州石化分公司 | Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process |
| CN103028419A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for low-water ratio ethylbenzene dehydrogenation |
| CN105777480A (en) * | 2014-12-15 | 2016-07-20 | 中国石油天然气股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
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