CN114452981B - Ethylbenzene dehydrogenation catalyst with ultralow water ratio and preparation method thereof - Google Patents
Ethylbenzene dehydrogenation catalyst with ultralow water ratio and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 181
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 238000004458 analytical method Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 27
- 229910001462 kalsilite Inorganic materials 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004876 x-ray fluorescence Methods 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- 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 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical class [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims 3
- 229910001940 europium oxide Inorganic materials 0.000 claims 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims 3
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims 3
- 229940075613 gadolinium oxide Drugs 0.000 claims 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims 3
- 235000012245 magnesium oxide Nutrition 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 claims 1
- 229910001930 tungsten oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 229910052700 potassium Inorganic materials 0.000 abstract description 13
- 239000011591 potassium Substances 0.000 abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 56
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 46
- 239000000203 mixture Substances 0.000 description 38
- 229910000027 potassium carbonate Inorganic materials 0.000 description 23
- 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 21
- 239000001768 carboxy methyl cellulose Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 21
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 21
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 20
- 239000001095 magnesium carbonate Substances 0.000 description 20
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DXDWSXBIERDUTF-UHFFFAOYSA-N [Mg].[W].[Ce].[K].[Fe] Chemical compound [Mg].[W].[Ce].[K].[Fe] DXDWSXBIERDUTF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- -1 rare earth compounds Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- 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
-
- 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
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- 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)
Abstract
The invention relates to an ethylbenzene dehydrogenation catalyst with an ultralow water ratio and a preparation method thereof, and mainly solves the problems of poor stability and low activity of a low-potassium catalyst under the condition of ultralow water ratio in the prior art. The invention adopts an ethylbenzene dehydrogenation catalyst with ultra-low water ratio, which comprises the following components in percentage by weight: 67-79% Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 6 to 10 percent of K 2 O, where K 2 5-35% of the weight amount of O is derived from kaliophene; 6-11% CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the 1 to 5 percent of WO 3 The method comprises the steps of carrying out a first treatment on the surface of the MgO in 0.5-5 wt%; 0.5-5% of intermediate rare earth oxide; the intermediate rare earth oxide is selected from Eu 2 O 3 、Gd 2 O 3 Or Dy (Dy) 2 O 3 At least one of (2); the surface of the obtained catalyst is K before and after the reaction 2 The technical proposal that the O content is reduced by 0.02 to 0.25 percent solves the problem well, and can be used in the industrial production of preparing styrene by ethylbenzene dehydrogenation under the condition of ultralow water ratio.
Description
Technical Field
The invention relates to a styrene catalyst prepared by ethylbenzene dehydrogenation with ultra-low water ratio and a preparation method thereof.
Background
The main reaction of ethylbenzene dehydrogenation is C 6 H 5 -C 2 H 5 →C 6 H 5 CH＝CH 2 +H 2 +124KJ/mol. Thermodynamically, lowering the ethylbenzene partial pressure is advantageous for equilibrium, so it is common in industry to add steam to drive the reaction toward the product. The latest development trend of the technology for producing styrene by ethylbenzene dehydrogenation is to reduce raw material consumption and improve energy efficiency. The vaporization latent heat of the water is great, and the phenyletheneThe alkene production process consumes a large amount of superheated steam as a dehydrogenation medium, so that the process has high energy consumption and high production cost. The development of low water ratio catalysts suitable for isothermal fixed beds with water ratios below 1.0 (by weight) to reduce industrial plant operating water ratios is an urgent need for styrene plants, particularly large styrene plants.
Iron-based catalysts which take ferric oxide as a main active component and potassium oxide as a main promoter are commonly used in the industrial ethylbenzene dehydrogenation production, and potassium can increase the activity of the ferric oxide by orders of magnitude, promote the water gas reaction to eliminate carbon deposit and automatically regenerate the catalysts. But on the surface of the catalyst particles, the auxiliary agent K 2 0 is easy to be combined with water vapor or by-product CO 2 Acting to form KOH or K 2 CO 3 And is carried away and lost, thereby affecting the self-regeneration capability and stability of the catalyst, and realizing low potassium content of less than 10 percent is the main stream of ethylbenzene dehydrogenation catalyst development.
In this regard, many attempts have been made according to the reports of the related literature so far. The ethylbenzene dehydrogenation catalyst with low water ratio of China patent 200510111471.0 reports that after at least two light rare earth compounds except cerium are added in a Fe-K-Ce-W system, the stability of the low-potassium catalyst under the condition of low water ratio of 1.8 (weight) is remarkably improved, and meanwhile, the catalyst has higher activity. As disclosed in us patent 4535067, a portion of the potassium in the catalyst was reported to be added as kaliophene, but the catalyst had a conversion of less than 65% at 614±2 ℃, a selectivity of 93% at most, and less than 60% singly, which was relatively low. Moreover, the lifetime of the catalyst is not involved.
With the large-scale of styrene units, energy conservation is becoming more and more important. Therefore, the use condition of the dehydrogenation catalyst is slightly improved, any equipment is not required to be changed, and investment is not required to be increased, so that a manufacturing enterprise can obtain great economic benefit. It has been a force of researchers to develop a low-potassium catalyst with higher activity suitable for operation under ultra-low water ratio conditions.
Disclosure of Invention
The invention aims to solve the technical problems of poor stability and low activity of a low-potassium catalyst under the condition of ultralow water ratio in the prior art, and provides a novel catalyst for preparing styrene by ethylbenzene dehydrogenation, which is used for ethylbenzene dehydrogenation reaction and has the characteristics of good stability and high activity under the condition of ultralow water ratio.
The second technical problem to be solved by the invention is to provide a preparation method of an ethylbenzene dehydrogenation catalyst with ultra-low water ratio corresponding to one of the technical problems.
The invention provides a method for preparing styrene by dehydrogenating ethylbenzene with ultralow water ratio, which corresponds to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: the catalyst comprises the following components: a first set of primary metal oxides, a second set of metal oxides, and a third set of metal oxides; the first group of main metal oxides are iron, potassium and cerium; the second group of metal oxides is tungsten, magnesium; the third group of metal oxides is at least one of europium, gadolinium or dysprosium.
In the technical proposal, based on the total amount of the ethylbenzene dehydrogenation catalyst, the first group of main metal oxides contains 67 to 79 percent of Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 6 to 10 percent of K 2 O, O; 6-11% CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The second group of metal oxides contains 1 to 5% of WO 3 The method comprises the steps of carrying out a first treatment on the surface of the MgO in 0.5-5 wt%; the third group of metal oxides contains 0.5 to 5% Eu 2 O 3 、Gd 2 O 3 And Dy 2 O 3 At least one of (a) and (b).
In the above technical scheme, the catalyst surface K after the reaction 2 The reduction rate of the O content is 0.2 to 4 percent, wherein K is 2 The reduction rate of the O content is K in the catalyst before the reaction 2 The O content and K obtained by X-ray fluorescence analysis (XRF) of the catalyst surface removed after the reaction 2 Difference in O content and K in the pre-reaction catalyst 2 Ratio of O content. Preferably post-reaction K 2 The reduction rate of the O content is 0.8-2.2%. More preferred post-reaction K 2 The reduction rate of the O content is 0.8-1.1%.
In the above technical scheme, the middleRare earth oxide is selected from Eu 2 O 3 、Gd 2 O 3 Or Dy (Dy) 2 O 3 The content of (2) is preferably 0.9 to 4%.
In the above technical scheme, the intermediate rare earth oxide preferably comprises Eu at the same time 2 O 3 And Gd 2 O 3 Or Eu 2 O 3 And Dy 2 O 3 Or Gd 2 O 3 And Dy 2 O 3 The two intermediate rare earth oxides have binary synergistic effect on the activity and stability of the catalyst under the ultra-low water ratio; more preferably at the same time Eu 2 O 3 、Gd 2 O 3 And Dy 2 O 3 At this time, the three kinds of intermediate rare earth oxides have ternary synergistic effect on the activity and stability of the catalyst under the ultra-low water ratio.
In the above technical scheme, the catalyst preferably does not contain molybdenum oxide.
In the above technical scheme, the catalyst preferably contains no binder, and the binder comprises kaolin, diatomite and cement.
In the technical proposal, the Fe is calculated by weight percent 2 O 3 Preferably from iron oxide red and iron oxide yellow, preferably in the proportions of iron oxide red: iron oxide yellow=2.5-4.5:1.
In the technical proposal, K is used for 2 From 5 to 35% by weight of K in the catalyst, based on the total amount of O 2 O is derived from kalsilite, preferably 10 to 30% by weight K 2 O is derived from kaliophlomis.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps: and uniformly contacting the Fe source, the K source, the Ce source, the W source, the Mg source, the intermediate rare earth oxide and the pore-forming agent which are weighed according to the proportion with water, and extruding, drying and roasting to obtain the catalyst. Preferably, the water is added in an amount of 15 to 35% by weight based on the total weight of the catalyst raw material.
In the above technical scheme, ce is preferably added in the form of cerium oxalate or cerium acetate.
In the technical scheme, the three-step method is adopted for drying, namely, the temperature is 30-50 ℃ for 1-4 hours, the temperature is 70-90 ℃ for 1-4 hours, and the temperature is 125-155 ℃ for 1-4 hours.
In the technical scheme, the roasting temperature is 550-980 ℃, and the roasting time is 2-8 hours.
In the above technical scheme, as a preferable roasting condition, the roasting temperature is gradually increased, for example, but not limited to, roasting at 550-650 ℃ for 1-4 hours, and then roasting at 880-980 ℃ for 1-4 hours.
In order to solve the third technical problem, ethylbenzene is used as raw material, the reaction temperature is 590-640 ℃, and the liquid space velocity is 1.2-1.8 hours －1 The water ratio (weight) is 0.7-1.0, the pressure is-70 to-30 KPa, and the raw material is contacted and reacted with an ethylbenzene dehydrogenation catalyst with ultra-low water ratio to obtain the styrene.
The raw materials used for the catalyst component of the invention are as follows:
fe used 2 O 3 Adding in the forms of iron oxide red and iron oxide yellow; k is prepared from potassium carbonate and kalioplast (KAlSiO) 4 ) Adding in a form; the W used is added in the form of its salts or oxides; the Mg is added in the form of oxide, hydroxide or carbonate; the remaining elements are added in oxide form. In the preparation process of the invention, besides the main catalyst component, a pore-forming agent is added, wherein the pore-forming agent can be selected from graphite, polystyrene microspheres or sodium carboxymethyl cellulose, and the addition amount of the pore-forming agent is 2.5-6.5% of the total weight of the catalyst.
X-ray fluorescence analysis (XRF) was performed on PW 2404X-ray fluorescence spectrometer from PHILIPS, netherlands, with an angular accuracy of 0.0025 °; the repeatability of 2 theta angle is 0.0001 degree, and the scanning speed 2 theta is 0.0001-2 degrees/s. K (K) 2 The reduction rate of the O content is K in the catalyst before the reaction 2 The O content (see Table 1) and the K obtained by X-ray fluorescence analysis (XRF) of the catalyst surface removed after the reaction 2 The difference in O content (see Table 2) and K in the pre-reaction catalyst 2 Ratio of O content. . The content of each component in the catalyst before the reaction is uniformly distributed, and K in the catalyst 2 O content and catalyst surface K 2 The O content is the same. The active components in the catalyst are lost and migrated after the reaction, and K on the surface of the catalyst after the reaction 2 The trend of the decrease rate of the O content reflects the stability of the catalyst. Wherein the reaction is followed by a stable operation reaction of the catalyst for 1000 hours or more in the prior art.
The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed, and the process is briefly described as follows for the activity evaluation of the catalyst for preparing styrene by ethylbenzene dehydrogenation:
deionized water and ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gaseous state, and then enter into a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reactor was internally filled with 100 ml of a catalyst having a particle diameter of 3 mm, which was a stainless steel tube having an inner diameter of 1 ". The reaction product flowing out of the reactor was condensed and analyzed for its composition by gas chromatography.
The ethylbenzene conversion and styrene selectivity were calculated according to the following formula:
the invention adds and selects the intermediate rare earth oxide Eu in kalsilite form by adopting partial potassium compound in the Fe-K-Ce-W-Mg catalytic system 2 O 3 、Gd 2 O 3 Or Dy (Dy) 2 O 3 On one hand, as kalioplast can be slowly decomposed under the condition of water vapor to provide a potassium source, the release speed of potassium is controlled, the migration and the loss speed of potassium are reduced, the removal of carbon deposit is continuously promoted, and the self-regeneration capability of the catalyst is enhanced; on the other hand, the alkalinity of the system is improved, the active phase of the catalyst is stabilized and dispersed, the electron transfer capability of the active phase is improved, and higher activity is facilitated. The catalyst prepared by the invention is used for evaluating the activity in an isothermal fixed bed, and the catalyst is used for controlling the pressure of liquid at-50 KPaThe usual 1.0 is increased to 1.4 hours －1 As evaluated under the conditions that the temperature is increased from the normal 620 ℃ to 630 ℃ and the water is reduced by 60 to 0.8 percent (weight) compared with the normal 2.0 (weight), the ethylbenzene conversion rate is up to 79.8 percent, the ethylbenzene conversion rate is reduced by 0.5 percent after the stable operation is carried out for 1500 hours, and the catalyst surface K is removed after the reaction 2 The O content is reduced by only 0.02%, the activity and stability of the low-potassium catalyst under the condition of ultralow water ratio are obviously improved, and a better technical effect is obtained.
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 (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, eu 1.68 parts 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
100 ml of catalyst was charged into the reactor at-50 KPa, liquid space velocity for 1.4 hours －1 The activity was evaluated at 630℃and a water ratio (by weight) of 0.8, and the results are shown in Table 2. The catalyst removed after 1600 hours of reaction was subjected to surface composition analysis on PW 2404X-ray fluorescence spectrometer from PHILIPS, netherlands, with an 2 theta angle accuracy of 0.0025 °;2 theta angle repeatability of 0.0001 degree, scanning speed 2 theta of 0.0001-2 degrees/s, and surface K 2 The results of the O content analysis are shown in Table 2.
Comparative example 1
In addition to K 2 O is derived from potassium carbonate, without Eu 2 O 3 Outside is provided withThe comparative example relationship, catalyst preparation method and catalyst evaluation conditions and analysis method of the remaining components were the same as those of example 1, and specifically:
will correspond to 57.67 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.53 parts of Fe 2 O 3 Iron oxide yellow of 9.71 parts of K 2 Potassium carbonate of O, equivalent to 9.06 parts of CeO 2 Is equivalent to 2.62 parts of WO 3 Stirring the ammonium tungstate, magnesium carbonate equivalent to 1.4 parts of MgO and 5.37 parts of sodium carboxymethyl cellulose in a kneader for 1.5 hours, adding deionized water accounting for 29.7 percent of the total weight of the catalyst raw material, stirring for 0.5 hour, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 6 mm, putting the particles into a baking oven, baking at 45 ℃ for 2 hours, baking at 75 ℃ for 2 hours, baking at 145 ℃ for 3 hours, putting the particles into a muffle furnace, baking at 590 ℃ for 2 hours, baking at 910 ℃ for 3 hours, and baking at 920 ℃ for 3 hours to obtain the finished catalyst, wherein the catalyst composition is shown in table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 2
In addition to K 2 The comparative relation of the components, the catalyst preparation method, the catalyst evaluation conditions and the analysis method were the same as those of example 1 except that all O was derived from potassium carbonate, specifically:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of 9.55 parts of K 2 Potassium carbonate of O, equivalent to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, eu 1.68 parts 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and catalyst detached after 1600 hours of reactionAgent surface K 2 The results of the O content analysis are shown in Table 2.
Example 2
Except with Gd 2 O 3 Replacement of Eu 2 O 3 The catalyst preparation method, catalyst evaluation conditions, and analysis method were the same as those of example 1, and specifically:
will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Magnesium carbonate corresponding to 1.38 parts MgO, 1.68 parts Gd 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 3
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of 9.55 parts of K 2 Potassium carbonate of O, equivalent to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Magnesium carbonate corresponding to 2.38 parts MgO, 0.45 parts Gd 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 7 hours at 145 ℃, then are put into a muffle furnace, baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in table 1.
Prepared as in example 1,Evaluation and analysis of the catalyst, test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 3
In addition to Dy 2 O 3 Replacement of Eu 2 O 3 The catalyst preparation method, catalyst evaluation conditions, and analysis method were the same as those of example 1, and specifically:
56.7 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts of MgO, 1.68 parts of Dy 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 4
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 parts of Eu was used 2 O 3 And 0.84 part Gd 2 O 3 Replacement of 1.68 parts Eu 2 O 3 。
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, 0.84 parts Eu 2 O 3 0.84 part of Gd 2 O 3 5.37 parts of sodium carboxymethylcellulose in a kneaderStirring for 1.5 hours, adding deionized water accounting for 29.7 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 mm and the length of 6 mm, putting into a baking oven, baking at 45 ℃ for 2 hours, baking at 75 ℃ for 2 hours, baking at 145 ℃ for 3 hours, putting into a muffle furnace, baking at 590 ℃ for 2 hours, and baking at 910 ℃ for 3 hours to obtain the finished catalyst, wherein the catalyst composition is shown in table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 5
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 parts of Eu was used 2 O 3 And 0.84 part Dy 2 O 3 Replacement of 1.68 parts Eu 2 O 3 。
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, 0.84 parts Eu 2 O 3 0.84 part Dy 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 6
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 parts of Gd was used 2 O 3 And 0.84 part Dy 2 O 3 Replacement of 1.68 parts Eu 2 O 3 。
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent of 19.2 partsFe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Magnesium carbonate corresponding to 1.38 parts MgO, 0.84 parts Gd 2 O 3 0.84 part Dy 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 7
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.56 parts of Eu was used 2 O 3 0.56 part of Gd 2 O 3 And 0.56 part Dy 2 O 3 Replacement of 1.68 parts Eu 2 O 3 。
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, 0.56 parts Eu 2 O 3 0.56 part of Gd 2 O 3 0.56 part Dy 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1. Test results and removal after 1600 hours of reactionCatalyst surface K 2 The results of the O content analysis are shown in Table 2.
Example 8
Will correspond to 53.88 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 17.05 parts of Fe 2 O 3 Iron oxide yellow of 6.91 parts of K 2 Potassium carbonate of O, equivalent to 0.94 parts of K 2 Kalsilite of O corresponds to 10.4 parts of CeO 2 Is equivalent to 4.13 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 3.35 parts MgO, eu 2.85 parts 2 O 3 0.49 part of ZrO 2 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 9
Will correspond to 54.59 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 12.45 parts of Fe 2 O 3 Iron oxide yellow of 6.13 parts of K 2 Potassium carbonate of O, equivalent to 2.62 parts of K 2 Kalsilite of O corresponds to 10.55 parts of CeO 2 Cerium oxalate equivalent to 4.91 parts of WO 3 Ammonium tungstate, magnesium carbonate equivalent to 4.95 parts MgO, 3.8 parts Eu 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
Prepared and evaluated as in example 1Valence and analysis of the catalyst, test results and catalyst surface K detached after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 4
Will correspond to 56.89 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 15.94 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 5.33 parts of K 2 Potassium carbonate of O, equivalent to 0.22 part of K 2 Kalsilite of O corresponds to 8.55 parts of CeO 2 Is equivalent to 2.71 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 4.95 parts MgO, 3.9 parts Eu 2 O 3 1.51 parts of MoO 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 5
Will correspond to 55.36 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 17.42 parts of Fe 2 O 3 Iron oxide yellow of (3.71 parts of K) 2 Potassium carbonate of O, equivalent to 2.14 parts of K 2 Kalsilite of O corresponds to 8.04 parts of CeO 2 Is equivalent to 4.82 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 2.53 parts MgO, 3.88 parts Eu 2 O 3 Stirring 2.1 parts of cement and 5.37 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 29.7 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 mm and the length of 6 mm, putting into a baking oven, baking at 45 ℃ for 2 hours, baking at 75 ℃ for 2 hours, baking at 145 ℃ for 3 hours, then putting into a muffle furnace, baking at 590 ℃ for 2 hours, baking at 910 ℃ for 3 hours to obtain a finished catalyst, and forming the catalystAre listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 10
Will correspond to 61.27 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 17.36 parts of Fe 2 O 3 Iron oxide yellow of (2) and equivalent to 4.59 parts of K 2 Potassium carbonate of O, equivalent to 2.16 parts of K 2 Kalsilite of O corresponds to 6.35 parts of CeO 2 Is equivalent to 4.75 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 0.55 part MgO, 2.97 parts Eu 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 6
Will correspond to 52.8 parts of Fe 2 O 3 Iron oxide red of (2) and equivalent to 23.1 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O, 8.91 parts CeO 2 Equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts MgO, eu 1.68 parts 2 O 3 And 5.37 parts of sodium carboxymethyl cellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, extruded into particles with the diameter of 3 mm and the length of 6 mm, the particles are extruded into particles with the diameter of 3 mm, and the particles are put into a baking oven, baked at 45 ℃ for 2 hours, baked at 75 ℃ for 2 hours and baked at 145 ℃ for 3 hours, and then put into a muffle furnace for baking at 590 ℃ for 2 hours, and baked at 910 ℃ for 3 hours to obtain the finished product of the catalystThe catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 11
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 7.16 parts of K 2 Potassium carbonate of O, equivalent to 2.39 parts of K 2 Kalsilite of O corresponds to 6.81 parts of CeO 2 Is equivalent to 1.21 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 2.38 parts MgO, and 4.15 parts Eu 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 12
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) corresponding to 5.14 parts of K 2 Potassium carbonate of O, equivalent to 1.71 parts of K 2 Kalsilite of O corresponds to 6.81 parts of CeO 2 Is equivalent to 2.58 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 3.98 parts MgO, eu 3.88 parts 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, extruded into particles with the diameter of 3 mm and the length of 6 mm, and the particles are put in a baking oven for 2 hours at 45 ℃,2 hours at 75 ℃ and 3 hours at 145 ℃, then are put in a muffle furnace for 2 hours at 590 DEG CRoasting at 910 ℃ for 3 hours 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, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Comparative example 7
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of 6.41 parts of K 2 Potassium carbonate of O, equivalent to 2.14 parts of K 2 Kalsilite of O corresponds to 7.75 parts of CeO 2 Is equivalent to 1.25 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.05 parts MgO, 5.5 parts Eu 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 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, particles with the diameter of 3 mm and the length of 6 mm are extruded, the particles are put into a baking oven, baked for 2 hours at 45 ℃, baked for 2 hours at 75 ℃ and baked for 3 hours at 145 ℃, then the particles are put into a muffle furnace and baked for 2 hours at 590 ℃ and baked for 3 hours at 910 ℃ to obtain the finished catalyst, and the catalyst composition is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
Example 13
Will correspond to 56.7 parts Fe 2 O 3 Iron oxide red of (2) and equivalent to 19.2 parts of Fe 2 O 3 Iron oxide yellow of (2) and equivalent to 8.79 parts of K 2 Potassium carbonate of O, equivalent to 0.76 part of K 2 Kalsilite of O corresponds to 8.91 parts of CeO 2 Is equivalent to 3.41 parts of WO 3 Ammonium tungstate, magnesium carbonate corresponding to 1.38 parts of MgO, 0.85 part of Dy 2 O 3 And 5.37 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 29.7 percent of the total weight of the catalyst raw material is added, the mixture is stirred for 0.5 hour, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6 mm, and the particles are put into a baking oven, baked at 45 ℃ for 2 hours, baked at 75 ℃ for 2 hours and baked at 145 ℃ for 3 hours and then put into a positionThe catalyst was calcined in a muffle furnace at 590℃for 2 hours and at 910℃for 3 hours to give a finished catalyst, the catalyst composition of which is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, with test results and catalyst surface K removed after 1600 hours of reaction 2 The results of the O content analysis are shown in Table 2.
TABLE 1
Table 1 (subsequent)
TABLE 2
The above examples illustrate the addition of a partial potassium compound as kalsilite and the selection of the medium rare earth oxide Eu in an iron-potassium-cerium-tungsten-magnesium catalytic system 2 O 3 、Gd 2 O 3 Or Dy (Dy) 2 O 3 The obtained catalyst has strong automatic regeneration capability, improves the activity and stability of the low-potassium catalyst under the condition of ultralow water ratio, has obvious energy-saving effect, is beneficial to the cost reduction and efficiency enhancement of a styrene device, and can be used in the industrial production of preparing styrene by ethylbenzene dehydrogenation under the condition of ultralow water ratio.
Claims (7)
1. The ethylbenzene dehydrogenation catalyst is characterized by comprising a first group of main metal oxides, a second group of metal oxides and a third group of metal oxides; the first group of main metal oxides are iron oxides, potassium oxides and cerium oxides; the second group of metal oxides are tungsten oxides and magnesium oxides; the third group of metal oxides are at least two of europium oxide, gadolinium oxide and dysprosium oxide;
the first group of main metal oxides contains 67 to 79 percent of Fe based on the total amount of the ethylbenzene dehydrogenation catalyst 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 6 to 10 percent of K 2 O; 6-11% CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The second group of metal oxides contains 1 to 5% of WO 3 The method comprises the steps of carrying out a first treatment on the surface of the MgO in 0.5-5 wt%; the third group of metal oxides contains 0.5 to 5% Eu 2 O 3 、Gd 2 O 3 And Dy 2 O 3 At least two of (2);
in K 2 From 5 to 35% by weight of K in the catalyst, based on the total amount of O 2 O is derived from kalsilite;
the catalyst is prepared according to a preparation method comprising the following steps:
uniformly contacting at least two of a Fe source, a K source, a Ce source, a W source, a Mg source, a europium oxide, a gadolinium oxide and a dysprosium oxide and a pore-forming agent according to a proportion with water, and extruding, drying and roasting to obtain the catalyst;
wherein the three-step method is adopted for drying, namely, the temperature is 30-50 ℃ for 1-4 hours, the temperature is 70-90 ℃ for 1-4 hours, and the temperature is 125-155 ℃ for 1-4 hours;
wherein, the roasting is that the material is roasted for 1 to 4 hours at 550 to 650 ℃, and then roasted for 1 to 4 hours at 880 to 980 ℃;
the ultra-low water ratio is 0.7-1.0 by weight of water ratio.
2. The ultra-low water ratio ethylbenzene dehydrogenation catalyst according to claim 1, wherein the catalyst surface K is after the reaction 2 The reduction rate of the O content is 0.2 to 4 percent, wherein the K is 2 The reduction rate of the O content is K in the catalyst before the reaction 2 The O content and K obtained by X-ray fluorescence analysis (XRF) of the catalyst surface removed after the reaction 2 Difference in O content and K in the pre-reaction catalyst 2 Ratio of O content.
3. The ultra-low water ratio ethylbenzene dehydrogenation catalyst according to claim 1, wherein the content of the third group of metal oxides is 0.9-4%.
4. An ultra-low water ratio ethylbenzene dehydrogenation catalyst according to any one of claims 1-3 characterized by the fact that it is prepared in the form of a catalyst having a specific molecular weight of K 2 From 10 to 30% by weight of K in the catalyst, based on the total amount of O 2 O is derived from kaliophlomis.
5. The process for preparing an ultra-low water ratio ethylbenzene dehydrogenation catalyst as claimed in any one of claims 1 to 4 comprising the steps of: uniformly contacting at least two of a Fe source, a K source, a Ce source, a W source, a Mg source, a europium oxide, a gadolinium oxide and a dysprosium oxide and a pore-forming agent according to a proportion with water, and extruding, drying and roasting to obtain the catalyst;
wherein the three-step method is adopted for drying, namely, the temperature is 30-50 ℃ for 1-4 hours, the temperature is 70-90 ℃ for 1-4 hours, and the temperature is 125-155 ℃ for 1-4 hours;
wherein the calcination is performed at 550-650 ℃ for 1-4 hours, and then at 880-980 ℃ for 1-4 hours.
6. The process according to claim 5, wherein the Ce source is added as cerium oxalate or cerium acetate.
7. A method for preparing styrene by ethylbenzene dehydrogenation, which adopts the catalyst of any one of claims 1-4 or the catalyst prepared by the preparation method of any one of claims 5-6, takes ethylbenzene as raw material, and has the reaction temperature of 590-640 ℃ and the liquid space velocity of 1.2-1.8 hours -1 The water ratio by weight is 0.7-1.0, the pressure is-70 to-30 kPa, and the raw material is contacted and reacted with the ethylbenzene dehydrogenation catalyst with ultra-low water ratio to obtain the styrene.
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