CN116726919B - Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof - Google Patents
Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof Download PDFInfo
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- CN116726919B CN116726919B CN202310576427.5A CN202310576427A CN116726919B CN 116726919 B CN116726919 B CN 116726919B CN 202310576427 A CN202310576427 A CN 202310576427A CN 116726919 B CN116726919 B CN 116726919B
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000005977 Ethylene Substances 0.000 title claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- 230000001590 oxidative effect Effects 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 45
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 150000003282 rhenium compounds Chemical class 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- -1 alcohol amine Chemical class 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000004684 trihydrates Chemical class 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- RKGLUDFWIKNKMX-UHFFFAOYSA-L dilithium;sulfate;hydrate Chemical compound [Li+].[Li+].O.[O-]S([O-])(=O)=O RKGLUDFWIKNKMX-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A modified carrier of an ethylene oxide catalyst synthesized by ethylene oxidation and a preparation method thereof, which belong to the technical field of catalyst preparation. Adopting alpha-Al with certain granularity 2 O 3 The powder is directly modified to synthesize the catalyst carrier, and the synthesized carrier has uniform microscopic particle size and reasonable pore canal structure, and has better activity and selectivity when being used for preparing the ethylene oxide silver catalyst. And the carrier has high strength, is not easy to pulverize, and prolongs the service life of the catalyst. alpha-Al used in the Carrier 2 O 3 The powder is calcined at high temperature, so that the content of acid sites on the surface is greatly reduced, and the situation of carbon deposition can be reduced after the catalyst is synthesized, thereby being more beneficial to the improvement of the stability of the catalyst.
Description
Technical Field
The invention relates to a modified carrier of an ethylene oxide catalyst prepared by oxidizing ethylene and a preparation method thereof, belonging to the technical field of catalyst preparation.
Background
At present, the existing ethylene oxidation synthesis ethylene oxide silver catalyst mainly adopts alpha-alumina as a carrier, most of raw materials for synthesizing the carrier are alumina trihydrate (namely aluminum hydroxide), pseudo-alumina monohydrate, pseudo-boehmite and the like, and the alpha-phase alumina is formed after molding and high-temperature calcination and crystal transformation. However, in the process of forming alpha-alumina by converting alumina, very high calcination temperatures (higher than 1500 ℃) are required, and the synthesis conditions of the carrier are severe. Although some researches can reduce the crystal transformation temperature by adding mineralizer, there is still incomplete crystal phase structure, which leads to non-uniform microscopic particle size and larger pore size grading of the carrier, thereby affecting the selectivity of the reaction of synthesizing ethylene oxide by ethylene oxidation. In addition, the existing carrier has lower strength, is easy to pulverize in the use process, and affects the service life of the catalyst.
Disclosure of Invention
To solve the problems existing in the prior art, alpha-Al with a certain granularity is adopted 2 O 3 The powder is directly modified to synthesize the catalyst carrier, and the synthesized carrier has uniform microscopic particle size and reasonable pore canal structure, and has better activity and selectivity when being used for preparing the ethylene oxide silver catalyst. And is also provided withThe carrier has high strength, is not easy to pulverize, and prolongs the service life of the catalyst.
The invention adopts the technical scheme that:
a modified support for an ethylene oxide catalyst for the oxidation of ethylene, the modified support comprising:
the modified alpha-Al 2 O 3 The preparation method of the powder comprises the following steps:
alpha-Al 2 O 3 Adding the powder into sodium metaaluminate solution, reacting at 50-120 deg.c for 30-120 min with alpha-Al 2 O 3 The mass ratio of the powder to the sodium metaaluminate is 2:1-6:1, the mass percentage of the sodium metaaluminate solution is 5-30%, and CO is introduced into the solution 2 Filtering until the pH value of the solution is 7.0-8.5, washing the powder until the electric conductivity of the washing water is less than 200 mu s/cm, drying and grinding to obtain the modified alpha-Al 2 O 3 Powder;
the alpha-Al 2 O 3 Specific surface area of the powder is 2-3 m 2 G, the granularity is 0.5-5 mu m;
the metal salt is one or more of magnesium, calcium, strontium, barium and zirconium;
the preparation method of the modified carrier comprises the following steps:
mixing the components according to the proportion of the carrier, pouring the mixture into a kneader, adding 10 to 50 parts of acid liquor for kneading, and kneading the materials into a paste, wherein the mass concentration of the acid liquor is 5 to 40 percent; and molding the kneaded material, drying the molded carrier for 12-36 h at 80-150 ℃, and calcining for 3-10 h at 1000-1500 ℃ to obtain the modified carrier of the catalyst. The silicon-containing compound is silica sol, white carbon black or water glass.
The binder is sesbania powder, cellulose and guar gum.
The metal salt is nitrate, sulfate, acetate or carbonate containing magnesium, calcium, strontium, barium and zirconium. The acid liquor is nitric acid or acetic acid.
The material is formed into a strip shape, a column shape or a ring shape, the length is 4-10 mm, and the diameter is 4-10 mm;
the specific surface area of the modified carrier is 0.5-2.0 m 2 And/g, water absorption of 30-60% and crushing strength of 200-500N/granule.
A method for preparing a catalyst from a modified support comprising the steps of:
1) Preparing an impregnating solution: complexing silver salt with organic amine, adding soluble rhenium compound and soluble alkali metal auxiliary agent to prepare aqueous solution;
wherein, NH in the organic amine complex silver salt 3 And Ag in a molar ratio of 0.8:1-1.5:1; the mass concentration of Ag in the impregnating solution is 5-30%, and the mass concentration of rhenium is 50-2000 ppm; the total concentration of metal ions of the soluble alkali metal auxiliary agent is 50-3000 ppm;
2) Dipping: weighing a modified carrier, measuring an impregnating solution according to the water absorption rate and the metal loading amount of the carrier, immersing the carrier in the impregnating solution, and immersing the carrier in the impregnating solution for 30-180 min after the carrier is adsorbed by the impregnating solution;
3) Filtering out more catalyst after soaking than soaking liquid, and stoving at 80-150 deg.c;
4) And activating the dried catalyst in air flow at 200-400 ℃ for 1-60 min to obtain the catalyst. The organic amine in the organic amine complex silver salt is aliphatic amine, alcohol amine or amide, and the silver salt is nitrate, acetate or oxalate;
the soluble rhenium compound is perrhenic acid or perrhenic acid ammonia, and the soluble alkali metal auxiliary agent is one or more of nitrate, acetate, sulfate and oxalate of lithium, sodium, potassium, rubidium and cesium.
It is emphasized that α -Al as used in the present application 2 O 3 Powder: specific surface area of 2-3 m 2 And/g, and the granularity is 0.5-5 mu m.
Further to the above alpha-Al 2 O 3 Powder modification: alpha-Al 2 O 3 Adding the powder into sodium metaaluminate solution, reacting at 50-120 deg.c for 30-120 min with alpha-Al 2 O 3 The mass ratio of the powder to the sodium metaaluminate is 2:1-6:1, the concentration of the sodium metaaluminate is 5-30%, and CO is introduced into the solution 2 Until the pH value of the solution is 7.0-8.5, filtering, washing the powder until the conductivity of the washing water is less than 200 mu s/cm, and drying and grinding for later use.
The method for further forming the carrier comprises the following steps:
1) Preparation of the Mixed Material per 100g of modified alpha-Al 2 O 3 The following materials are added into the powder:
a: the compound containing magnesium, calcium, strontium, barium and zirconium can be nitrate, sulfate, acetate and carbonate, and one or more of the compounds are added to be mixed, and the total amount is 0.1-10 g;
b: the silicon-containing compound can be silica sol, white carbon black and water glass, and the weight of the silicon-containing compound is 0.1-2 g of silicon oxide; c: the adhesive can be sesbania powder, cellulose and guar gum, and the weight of the adhesive is 1-10 g;
several materials are added into a mixer to be mixed uniformly.
2) Pouring the mixed materials into a kneader, adding 10-50 g of acid liquor for kneading, and kneading the materials into a paste, wherein the mass concentration of the acid liquor is 5-40%, and the acid liquor can be nitric acid or acetic acid;
3) Molding the kneaded material, wherein the kneaded material can be strip-shaped, columnar or annular, and has the length of 4-10 mm and the diameter of 4-10 mm;
4) Drying the molded carrier for 12-36 h at 80-150 ℃, and calcining for 3-10 h at 1000-1500 ℃ to obtain a catalyst carrier;
5) The main indexes of the carrier are as follows: specific surface area of 0.5-2.0 m 2 And/g, water absorption of 30-60% and crushing strength of 200-500N/granule.
Further, the catalyst synthesis method comprises the following steps:
1) Preparing an impregnating solution: an organic amine complex silver salt is adopted, and a soluble rhenium compound and a soluble alkali metal auxiliary agent are added to prepare an aqueous solution.
A: the organic amine may be aliphatic amine, alcohol amine or amide, wherein NH 3 And Ag in a molar ratio of 0.8:1-1.5:1;
b: the mass concentration of Ag in the impregnating solution is 5% -30%, and silver salt can be nitrate, acetate or oxalate; c: the soluble rhenium compound can be perrhenic acid or perrhenic acid ammonia, and the mass concentration of rhenium is 50-2000 ppm; d: the soluble alkali metal auxiliary agent can be one or more of nitrate, acetate, sulfate and oxalate of lithium, sodium, potassium, rubidium and cesium, and the total concentration of metal ions is 50-3000 ppm;
2) Dipping: weighing a certain mass of molded carrier, weighing a certain volume of impregnating solution according to the water absorption rate and metal loading capacity of the carrier, immersing the carrier in the impregnating solution, and immersing the carrier in the impregnating solution for 30-180 min after the carrier is adsorbed by the impregnating solution;
3) Filtering out more catalyst after soaking than soaking liquid, and stoving at 80-150 deg.c;
4) And activating the dried catalyst in air flow at 200-400 ℃ for 1-60 min to obtain the catalyst.
The beneficial effects of the invention are as follows:
1) In the present application, alpha-Al with limited particle size and specific surface area is directly adopted 2 O 3 The powder is modified to be used as a synthesized catalyst carrier, and alpha-phase alumina is formed after high-temperature calcination and crystal transformation after molding of alumina trihydrate. The alumina carrier has uniform microscopic particle size and reasonable pore canal structure, is more beneficial to the diffusion of reactants and products, and effectively improves the activity and selectivity of the catalyst.
2)α-Al 2 O 3 After the powder is modified, the specific surface area of the carrier is 0.5-2.0 m by combining a molding process 2 And/g, water absorption of 30-60% and crushing strength of 200-500N/granule. The strength of the modified carrier is far greater than that of the carrier in the prior art (about 100N/particle), the carrier is not easy to pulverize, and the service life of the catalyst is prolonged.
3) alpha-Al as used in the present application 2 O 3 The powder is calcined at high temperature and the surface acid is obtainedThe content of sex bits is greatly reduced, so that the situation of carbon deposition can be reduced after the catalyst is synthesized, and the stability of the catalyst is improved more favorably.
Drawings
FIG. 1 is a microstructure of the carrier in example 1.
FIG. 2 is a microstructure of the carrier of comparative example 1.
FIG. 3 is a microstructure of the carrier of comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
weighing alpha-Al with granularity of 1 μm 2 O 3 800g of powder is added into a reaction kettle to prepare 10 percent sodium metaaluminate solution according to alpha-Al 2 O 3 The mass ratio of the powder to the sodium metaaluminate is 2.5:1, 10 percent of sodium metaaluminate solution is put into a reaction kettle, the temperature is raised to 80 ℃, and CO is introduced into the solution after stirring for 1h 2 Adjusting the pH value of the solution to 7.5, filtering, washing the powder until the conductivity of the washing water is less than 200 mu s/cm, and drying and grinding for later use;
500g of modified alpha-Al is taken 2 O 3 Powder, zirconium oxide powder 7g, magnesium nitrate hexahydrate crystal 9.6g, barium sulfate powder 1.7g, white carbon black 1g and sesbania powder 25g are added into a mixer to be uniformly mixed;
pouring the mixed materials into a kneader, adding 120g of nitric acid solution with the mass concentration of 30%, kneading the materials into paste, forming, namely annular particles with the size of 8mm and the inner diameter of 2.5mm and the length of 8mm, drying the particles at 120 ℃ for 24 hours, and roasting at 1280 ℃ for 5 hours to obtain the catalyst carrier.
278.5g of ethylenediamine is weighed, 300g of water is added for dissolution, 396.83g of silver oxalate material containing 63% of silver is added into the solution, the temperature is kept below 30 ℃, 1.1g of ammonium perrhenate, 1.3g of cesium acetate and 3.4g of lithium sulfate monohydrate are added, stirring and dissolution are carried out, and water is added to the total weight of 1Kg, so that an impregnating solution with 25% of silver is obtained for standby.
Taking 200g of formed alumina carrier, placing into a pressure kettle for sealing, vacuumizing to below-0.09 Mpa, sucking impregnating solution without overload, placing into normal pressure for impregnating for 60min, filtering out excessive impregnating solution, drying at 100 ℃ for 5h, activating for 10min at 300 ℃ under flowing air, and cooling to obtain the required catalyst.
Comparative example 1:
alpha-Al of 1 mu m 2 O 3 800g of powder is added into a reaction kettle, 300g of pure water is added, the temperature is raised to 80 ℃ and the mixture is stirred for 1h, filtered, washed and dried, and then crushed for standby. The catalyst was prepared by the method for synthesizing the catalyst of example 1 using the above-mentioned powder synthesis support.
Comparative example 2:
adding 800g of commercial alumina trihydrate powder into a reaction kettle to prepare 10% sodium metaaluminate solution according to Al in the alumina trihydrate 2 O 3 The mass ratio of the content to the sodium metaaluminate is 2.5:1, 10 percent of sodium metaaluminate solution is put into a reaction kettle, the temperature is raised to 80 ℃, and CO is introduced into the solution after stirring for 1h 2 The pH value of the solution is regulated to 7.5, and after filtration, the powder is washed until the conductivity of washing water is less than 200 mu s/cm, and the powder is dried and crushed for standby. The catalyst was prepared by the method for synthesizing the catalyst of example 1 using the above-mentioned powder synthesis support.
Example 2
The catalyst was prepared in the same manner as in example 1, using alpha-Al having a particle size of 3. Mu.m 2 O 3 And (3) powder.
Examples 3 to 4
The catalyst was prepared in the same manner as in example 1, except for alpha-Al alone 2 O 3 The mass ratio of the powder to the sodium metaaluminate was 3.5:1 (example 3) and 4.5:1 (example 4).
Example 5
The catalyst was prepared in the same manner as in example 1, with a concentration of 20% sodium metaaluminate solution.
Examples 6 to 7
The catalyst was prepared in the same manner as in example 1, with the pH of the solution adjusted to 8.0 (example 6) and 8.5 (example 7).
Table 1 example and comparative example molded carrier properties
As can be seen from the above table, CO 2 Adjusting the pH value of the solution to ensure that the sodium metaaluminate is in alpha-Al as much as possible 2 O 3 The surface forms a precipitate, and the pH value after the reaction is not more than 8.5. Meanwhile, the carrier strength of the modified carrier is far higher than that of the comparative examples 1 and 2, the powder is not easy to pulverize, and the service life of the catalyst is prolonged.
Examples 8 to 9
The catalyst was prepared in the same manner as in example 1 except that the concentration of rhenium element was 1146ppm (example 8) and the concentration of the alkali metal element was 1904ppm (example 9).
Catalyst evaluation method: a fixed bed reactor (with an inner diameter of 10mm and a height of 50 cm), wherein the catalyst is crushed into particles with 12-16 meshes, and the filling amount is 3 mL;
reaction conditions: gas space velocity 5000h -1 The reaction temperature is 190-250 ℃, and the reaction pressure is 2.0Mpa;
raw material gas composition: ethylene concentration 25%, oxygen concentration 7%, CO 2 Concentration is 1%, dichloroethane inhibitor is 0.1-3 ppm, balance gas N 2 。
Table 2 evaluation results of catalysts
Although the present invention has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present invention.
Claims (9)
1. A modified carrier of an ethylene oxide catalyst for synthesizing ethylene oxide by ethylene oxidation is characterized in that:
the modified carrier component comprises:
the modified alpha-Al 2 O 3 The preparation method of the powder comprises the following steps:
alpha-Al 2 O 3 Adding the powder into sodium metaaluminate solution, reacting at 50-120 deg.c for 30-120 min with alpha-Al 2 O 3 The mass ratio of the powder to the sodium metaaluminate is 2:1-6:1, the mass percentage of the sodium metaaluminate solution is 5-30%, and CO is introduced into the solution 2 Filtering until the pH value of the solution is 7.0-8.5, washing the powder until the electric conductivity of the washing water is less than 200 mu s/cm, drying and grinding to obtain the modified alpha-Al 2 O 3 Powder;
the alpha-Al 2 O 3 Specific surface area of the powder is 2-3 m 2 G, the granularity is 0.5-5 mu m;
the metal salt is one or more of magnesium, calcium, strontium, barium and zirconium;
the preparation method of the modified carrier comprises the following steps:
mixing the components according to the proportion of the carrier, pouring the mixture into a kneader, adding 10 to 50 parts of acid liquor for kneading, and kneading the materials into a paste, wherein the mass concentration of the acid liquor is 5 to 40 percent; and molding the kneaded material, drying the molded carrier for 12-36 h at 80-150 ℃, and calcining for 3-10 h at 1000-1500 ℃ to obtain the modified carrier of the catalyst.
2. The modified support of ethylene oxide catalyst for the oxidation synthesis of ethylene according to claim 1, wherein: the silicon-containing compound is silica sol, white carbon black or water glass.
3. The modified support of ethylene oxide catalyst for the oxidation synthesis of ethylene according to claim 1, wherein: the binder is sesbania powder, cellulose and guar gum.
4. The modified support of ethylene oxide catalyst for the oxidation synthesis of ethylene according to claim 1, wherein: the metal salt is nitrate, sulfate, acetate or carbonate.
5. The modified support of ethylene oxide catalyst for the oxidation synthesis of ethylene according to claim 1, wherein: the acid liquor is nitric acid or acetic acid.
6. The modified support of ethylene oxide catalyst for the oxidation synthesis of ethylene according to claim 1, wherein: the material is shaped into a strip, a column or a ring, the length is 4-10 mm, and the diameter is 4-10 mm.
7. A modified support for an ethylene oxide catalyst for the oxidation of ethylene to ethylene according to any one of claims 1 to 6, characterized in that: the specific surface area of the modified carrier is 0.5-2.0 m 2 And/g, water absorption of 30-60% and crushing strength of 200-500N/granule.
8. The method for preparing a catalyst by modifying a carrier according to claim 7, wherein:
1) Preparing an impregnating solution: complexing silver salt with organic amine, adding soluble rhenium compound and soluble alkali metal auxiliary agent to prepare aqueous solution;
wherein, NH in the organic amine complex silver salt 3 And Ag in a molar ratio of 0.8:1-1.5:1; the mass concentration of Ag in the impregnating solution is 5-30%, and the mass concentration of rhenium is 50-2000 ppm; the total concentration of metal ions of the soluble alkali metal auxiliary agent is 50-3000 ppm;
2) Dipping: weighing a modified carrier, measuring an impregnating solution according to the water absorption rate and the metal loading amount of the carrier, immersing the carrier in the impregnating solution, and immersing the carrier in the impregnating solution for 30-180 min after the carrier is adsorbed by the impregnating solution;
3) Filtering out more catalyst after soaking than soaking liquid, and stoving at 80-150 deg.c;
4) And activating the dried catalyst in air flow at 200-400 ℃ for 1-60 min to obtain the catalyst.
9. The method for preparing a catalyst according to claim 8, wherein:
the organic amine in the organic amine complex silver salt is aliphatic amine, alcohol amine or amide, and the silver salt is nitrate, acetate or oxalate;
the soluble rhenium compound is perrhenic acid or perrhenic acid ammonia, and the soluble alkali metal auxiliary agent is one or more of nitrate, acetate, sulfate and oxalate of lithium, sodium, potassium, rubidium and cesium.
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