CN1162416C - Silver catalyst for epoxyethane production, its preparation method and application - Google Patents
Silver catalyst for epoxyethane production, its preparation method and application Download PDFInfo
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- CN1162416C CN1162416C CNB011443448A CN01144344A CN1162416C CN 1162416 C CN1162416 C CN 1162416C CN B011443448 A CNB011443448 A CN B011443448A CN 01144344 A CN01144344 A CN 01144344A CN 1162416 C CN1162416 C CN 1162416C
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- silver catalyst
- silver
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 84
- 239000004332 silver Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 229940100890 silver compound Drugs 0.000 claims description 12
- 150000003379 silver compounds Chemical class 0.000 claims description 12
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 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 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 150000002681 magnesium compounds Chemical class 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 4
- 239000000463 material Substances 0.000 claims 4
- 230000007420 reactivation Effects 0.000 claims 4
- 229940077744 antacid containing magnesium compound Drugs 0.000 claims 1
- 239000011233 carbonaceous binding agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 101150002998 LCAT gene Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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Images
Classifications
-
- 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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- Catalysts (AREA)
Abstract
The present invention relates to a silver catalyst for preparing epoxy ethane by oxidating ethylene. The silver catalyst is obtained through the following methods that a porous alpha-alumina carrier produced by baking at high temperature is impregnated by a solution prepared from silver-contained compounds, organic amine and various auxiliary agents; after leached and dried, the porous alpha-alumina carrier is activated with a gas mixture containing oxygen firstly; then, a catalyst precursor is processed with inert gases at proper temperature. The silver catalyst of the present invention has high and stable activity and selectivity.
Description
Technical field
The present invention relates to a kind of silver catalyst and preparation method thereof, more particularly the present invention relates to a kind of silver catalyst of producing by oxidation of ethylene in oxyethane and preparation method thereof that is used for, also relate to this catalyzer and produce purposes in the oxyethane at oxidation of ethylene.
Background technology
Oxidation of ethylene mainly generates oxyethane under the silver catalyst effect, side reaction takes place simultaneously generate carbonic acid gas and water, and wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity is meant temperature of reaction required when process for ethylene oxide production reaches certain reaction load.Temperature of reaction is low more, and activity of such catalysts is high more.So-called selectivity is meant that conversion of ethylene in the reaction becomes the ratio of the total reaction mole number of the mole number of oxyethane and ethene.So-called stability then is expressed as active and fall off rate optionally, and the fall off rate stability of small catalyst more is good more.The silver catalyst that uses high reactivity, highly selective and have good stability in the process of oxidation of ethylene production oxyethane can be increased economic efficiency greatly, and the silver catalyst of therefore making high reactivity, highly selective and good stability is the main direction of silver catalyst research.The performance of silver catalyst has the important relationship except that composition and the preparation method with catalyzer, and also the performance and the preparation method of the carrier that uses with catalyzer have important relationship.
In the prior art preparation method of silver catalyst comprise the preparation and administration to active ingredient of porous support (as aluminum oxide) and auxiliary agent to as described in this two processes on the carrier.
The ordinary method that active ingredient silver and auxiliary agent are applied on the carrier mainly is an immersion reduction method, promptly at first with the solution impregnating carrier that contains silver salt, organic amine and various auxiliary agents, then soaked carrier is carried out activation treatment so that silver salt is reduced into active ingredient silver in thermal medium, and excessive reductive agent is decomposed.
The activation phenomenon of introducing in the disclosed patent has air, contains oxygen gas mixture and inert atmosphere, and activation temperature is in 100～950 ℃ wide region.EP0038446A (EC ErdoelchemieGmbh, 1981) uses the method that progressively heats up to make silver compound resolve into active ingredient silver; The reduction temperature that US4400308A (EC Erdoelchemie Gmbh, 1983) uses is 400～500 ℃, and reducing atmosphere is the gas mixture that contains oxygen 4～21%; US4389338A (NipponShokubai Kagaku Kogyo Co., Ltd., 1983) oxygen level less than 3% inert atmosphere in, temperature is to handle soaked carrier under 600～800 ℃ the condition to make catalyzer in 20～90 minutes; The silver catalyst preparation process of JP62083041A report is to handle the shape of a saddle carrier of remaining silent that floods with silver salt, basic metal under inert atmosphere, 400～950 ℃ of conditions; US4837347A (Halcon SD Group, 1983) prepares silver catalyst in handling soaked carrier more than 400 ℃ in air; EP0161930A (Scientific Design Co., 1985) and EP0349229A (Scientific Design Co., 1990) flood auxiliary agents such as basic metal after proposing to handle the carrier of dipping silver in oxygen-containing atmosphere again; US5602070A (ScientificDesign Co., 1997) think and in being no more than 300 ℃ inert atmosphere, handle the performance that catalyzer helps improving catalyzer, US5736483A (Scientific Design Co., 1998) proposition activation temperature in air should not surpass 300 ℃, and activation temperature can be 400 ℃ in the inert atmosphere.
There is patent report under special conditions, to handle catalyzer and can obtains the ideal effect.JP56108533A (Nippon Shokubai Kagaku Kogyo Co., Ltd., 1981) propose in air, under 100～400 ℃ of conditions, to reduce silver compound, handle obtaining activity, selectivity and all higher catalyzer of stability again with carbonic acid gas in 50～400 ℃ down; US5502020A (Mitsubishi Petrochemical Co., Ltd., 1994) and EP0764464A2 (Mitsubishi Petrochemical Co., Ltd., 1997) propose in the impregnated carrier process, about 150 ℃, to handle carrier 15 minutes with superheated vapo(u)r, make the silver granuel uniform distribution, thermal treatment soaked carrier then prepares silver catalyst, and claims that this processing has improved activity of such catalysts, selectivity and stability.
Although above-mentioned patent documentation is all in the activity, selectivity and the stability that have improved the gained silver catalyst in varying degrees, this area still needs a kind of silver catalyst that comprehensively is improved and preparation method thereof on activity, selectivity and stability.
Summary of the invention
Situation in view of above-mentioned prior art, the present inventor has carried out research extensively and profoundly in the silver catalyst field, found that the solution that dipping is mixed with by silver compound, organic amine, various auxiliary agent on the porous heat-resistant carrier, through air or oxygen level less than 21% nitrogen oxygen atmosphere in behind the thermal treatment intermediate, use rare gas element once more the activity of the prepared silver catalyst of thermal treatment in ethylene oxidation reactions, selectivity and active and optionally stability all be improved.
Therefore, the purpose of this invention is to provide a kind of novel silver catalyst, it demonstrates good activity, selectivity and active and optionally stable in the process of oxidation of ethylene production oxyethane.
Another object of the present invention provides a kind of preparation method of above-mentioned silver catalyst.
A further object of the present invention provides the application of above-mentioned silver catalyst in oxidation of ethylene production oxyethane.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification sheets in conjunction with the accompanying drawings.
The accompanying drawing summary
Fig. 1 produces the graphic representation that concerns between the oxyethane total amount of temperature of reaction and generation in the process of oxyethane for the explanation sample of the embodiment of the invention and control sample at oxidation of ethylene; With
Fig. 2 produces the graphic representation that concerns between the oxyethane total amount of selectivity and generation in the process of oxyethane for the explanation sample of the embodiment of the invention and control sample at oxidation of ethylene.
Detailed Description Of The Invention
One aspect of the present invention provides a kind of Novel silver catalyst, and described catalyst is prepared by a method comprising the following steps:
1) usefulness contains the solution impregnation porous heat-resistant carrier of silver compound, organic amine and the various auxiliary agents of q.s;
2) elimination maceration extract, dry impregnated carrier;
3) in containing oxygen gas mixture to step 2) the gained carrier carries out primary activation;
4) directly or after cooling with inert gas to step 3) product heat-treat, make described silver catalyst.
The present invention relates to the application of above-mentioned novel silver catalyst in oxidation of ethylene production oxyethane on the other hand.
Porous heat-resistant carrier used according to the invention can be aluminum oxide, silicon carbide, silicon-dioxide or silica-alumina.Preferred main ingredient is α-Al
2O
3(α-Al for example
2O
3Account for more than 90%) porous α-Al
2O
3Carrier.
Porous α-the Al that is used for silver catalyst of the present invention
2O
3Carrier can be the porous alumina carrier through high-temperature roasting commonly used in the prior art.For example described porous α-Al
2O
3Carrier can be made as follows:
I) preparation has the mixture of following composition:
A) based on the mixture total weight amount be the low sodium three water α-Al of 30-64% weight
2O
3
B) based on the mixture total weight amount be the vacation one water α-Al of 5-39% weight
2O
3
C) based on the mixture total weight amount be the carbonaceous material of 5-30% weight;
D) based on the mixture total weight amount be the fusing assistant of 0.01-2.0% weight;
E) based on the mixture total weight amount be the fluoride-mineralization agent of 0.01-2.0% weight;
F) based on the mixture total weight amount be the binding agent of 25-59% weight; And
G) water of surplus;
Ii) with i) in the mixture that obtains mediate evenly and extrusion moulding; With
The iii) dry product that obtains in ii), at high temperature roasting becomes α-Al then
2O
3
In order to make carrier that enough intensity and good surface properties be arranged, preferably between 1250 ℃～1550 ℃, temperature is too high can to influence activity of such catalysts and the selectivity of making to maturing temperature, and the too low then support strength of maturing temperature is relatively poor.
The adding of fusing assistant is in order to make carrier have good intensity under low maturing temperature.The example of fusing assistant comprises magnesium compound, for example the mixture of one or more in magnesium oxide, sal epsom, magnesium nitrate and the magnesiumcarbonate.
The adding of carbonaceous material is in order to make macropore, thereby makes carrier have proper pore structure and specific surface.Described carbonaceous material comprises a kind of or its mixture in refinery coke, carbon dust, graphite, polyethylene, polypropylene, the rosin etc.Carbonaceous material is oxidation in roasting process, generates gas evolution, forms macropore in carrier.Granularity according to carbonaceous material of the present invention is 20～200 orders, and add-on is 5～30% weight of mixture total weight amount, preferred 10～25% weight, and adding too much can make the intensity of carrier obviously descend.
The fluoride-mineralization agent that the present invention selects for use comprises hydrogen fluoride, Neutral ammonium fluoride, aluminum fluoride, magnesium fluoride, sodium aluminum fluoride etc., and the crystal formation that its role is to promote the oxidation aluminium transforms, and eliminates the following pore of 5 μ m.
By adding binding agent, the vacation one water α-Al in it and the mixture
2O
3Generation aluminium colloidal sol bonds together each component, but becomes the paste of extrusion moulding.Used binding agent comprises acid, as nitric acid, formic acid, acetate, propionic acid and hydrochloric acid etc., and aluminium colloidal sol.When using acid as binding agent, salpeter solution preferably, wherein the weight ratio of nitric acid and water is 1: 1.25～10.
Can be dried to moisturely below 10% after the extrusion moulding of gained paste, support shapes can be annular, spherical, cylindricality or porous cylindricality.Drying temperature is 80～120 ℃, and be controlled at 1 hour～24 hour according to moisture content time of drying.
Dried paste makes aluminum oxide all be converted into α-Al 1250～1550 ℃ of following roastings 2～6 hours
2O
3The crushing strength of this carrier is 20N/ grain～120N/ grain, preferred 40N/ grain～80N/ grain; Specific surface is 0.1～2.0m
2/ g, preferred 0.5～1.5m
2/ g; Water-intake rate is not less than 40%, preferably is not less than 60%; Pore volume is 0.3-1.0ml/g, preferred 0.5-0.8ml/g; The aperture accounts for more than 90% of total pore volume greater than the hole of 1 μ m.
Silver catalyst of the present invention is by preparing with the above-mentioned alumina supporter of the solution impregnation of a kind of Ag-containing compound, organic amine and various auxiliary agents.
In the preparation of silver catalyst of the present invention, at first make the aqueous solution and the ammonium oxalate or the oxalic acid aqueous solution reaction of Silver Nitrate, separate out the silver oxalate precipitation, after the filtration, use deionized water wash, until no nitrate ion, then silver oxalate is dissolved in organic amine such as pyridine, butylamine, quadrol, 1, in the aqueous solution of 3-propylene diamine, thanomin or its mixture, add auxiliary agent, be made into dipping solution.Flood above-mentioned alumina supporter with the gained dipping solution then, drain, in being not more than 21% nitrogen oxygen atmosphere, airflow or oxygen level in 200～700 ℃, preferred 200-500 ℃ temperature range, kept 1 minute～120 minutes, and preferred 1 minute～60 minutes, to carry out thermolysis.Also available silver suboxide replaces Silver Nitrate, and silver oxalate also can not analysed filter, direct and organic amine complexing, impregnated carrier then.The amount of the silver compound that uses in the steeping process of the present invention should be enough to make argentiferous 1-30% weight in the finally prepd catalyzer, and preferred 5～25% weight are in total catalyst weight.
Auxiliary agent among the present invention can be compound or its mixture of alkali metal compound such as lithium, sodium, potassium, rubidium or caesium, and alkali-metal content is 100～1000ppm in the final catalyzer.Alkali metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
Auxiliary agent also can be the compound of alkaline earth metal compound such as calcium, strontium or barium, and the content of alkaline-earth metal is 50～1000ppm in the final catalyzer.Base earth metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
Impregnated in after silver compound on the carrier is heated decomposition, auxiliary agent also is applied on the carrier simultaneously, it is to heat-treat once more under 150～350 ℃ the condition in temperature that intermediate is placed rare gas element, treatment time is 1 minute～480 minutes, preferred 2 minutes～300 minutes, to improve catalyst performance.Described rare gas element is a pure inert gas, as nitrogen, helium or argon etc.
Various silver catalyst of the present invention is tested its performance with laboratory reaction device (to call " little anti-" in the following text) evaluating apparatus.Micro anti-evaluation device reaction device internal diameter 4mm, catalyst loading volume 1ml.The appreciation condition that the present invention uses is as follows:
Reactant gases is formed (mol%)
Ethene (C
2H
4) 20～32
Oxygen (O
2) 6.5～7.5
Carbonic acid gas (CO
2)＜10
Cause steady gas (N
2) surplus
Inhibitor ethylene dichloride 0.1ppm～7.0ppm
Reaction pressure 2.1MPa
Air speed 7000/h
Reactor outlet EO concentration 1.35% or 2.4%
Space-time yield 185 or 330kgEO/lCat./h
When stable reach above-mentioned reaction conditions after the METHOD FOR CONTINUOUS DETERMINATION reactor go into, exit gas forms.Measurement result carries out calculating as follows after volumetric shrinkage is proofreaied and correct selectivity:
Wherein Δ EO be work off one's feeling vent one's spleen poor with the inlet gas ethylene oxide concentration.Get the test-results of the mean number of 10 groups of above testing datas as the same day.
The present invention compares with prior art has following advantage: silver catalyst of the present invention is specially adapted to the reaction that oxidation of ethylene is produced oxyethane, shows higher, stable activity and selectivity in process of the test.
Embodiment
The present invention is described further below in conjunction with example, but scope of the present invention is not limited to these embodiment.
The preparation of carrier:
Get three water α-Al
2O
3312g, a false water α-Al
2O
392kg, refinery coke 81g, NH
4F7g, Mg (NO
3)
28.5g.
Put into blender and mix, change in the kneader, add rare nitric acid (nitric acid: water=1: 3) 0.18 liter, but be kneaded into the paste of extrusion moulding.Extrusion moulding is the three hole column form objects of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, more than 2 hours, free water content is reduced to below 10% 80～120 ℃ of oven dry.
Above-mentioned three hole column form objects are put into top-hat kiln, and through being elevated between 1450 ℃～1550 ℃ from room temperature about 30 hours, constant temperature 2 hours obtains white α-Al
2O
3Support samples.
After measured, the gained carrier has following performance:
Average intensity (N/ grain) 46
Specific surface (m
2/ g) 0.97
Water-intake rate (%) 73.5
Pore volume (ml/g) 0.72
Wherein＜1 the hole of μ m is 3.2%
Preparation of catalysts:
Getting the 1.4kg Silver Nitrate is dissolved in the 1.5l deionized water.Get in the deionized water that the 0.65kg ammonium oxalate is dissolved in 0.5l50 ℃.Under vigorous stirring, mix two kinds of solution, generate white silver oxalate precipitation.Aging more than 30 minutes, filter, be precipitated to no nitrate ion with deionized water wash.Filter cake argentiferous about 60%, moisture about 15%.
In the Glass Containers that band stirs, add the 0.6kg quadrol, 0.22kg thanomin, 0.75kg deionized water.Stir following silver oxalate paste that makes and slowly add in the mixed solution, temperature remains on below 40 ℃, and silver oxalate is all dissolved, and the add-on of silver oxalate makes steeping fluid argentiferous 22% weight that makes.Add the 3.5g cesium oxalate then, the 3.5g barium acetate adds the 0.5kg deionized water again, makes solution for later use.
Get support samples and put into the container that can vacuumize.Be evacuated to below the 10mmHg, put into above steeping fluid, the submergence carrier kept 30 minutes.Superfluous solution is removed in leaching.Soaked carrier heated 5 minutes in 200 ℃ airflow, cooling.
The catalyzer that makes above is divided into 3 parts, and a copy of it is sample in contrast, in addition two parts stand-by.
Embodiment 1
One duplicate samples is placed the cast container, feed nitrogen from bottom to top, airflow rate is 100ml/min, and container is heated to 250 ℃, keeps 4 hours, obtains final catalyst prod.
Embodiment 2
A remaining duplicate samples is handled by the same way as of embodiment 1, and different is that the gas and changing that will feed is an argon gas.
Embodiment 3～8
Prepare alumina supporter and silver catalyst as stated above, and be divided into 4 parts, handle by the same way as of embodiment 1, different is treatment time and treatment temp, and actual conditions sees Table 1.
Table 1 silver catalyst heat treatment test result
| Sample number into spectrum | Handle atmosphere | Treatment temp (℃) | Treatment time (minute) | Test result | |
| Temperature of reaction (℃) | Selectivity (%) | ||||
| Comparative example | ?216 | ?83.0 | |||
| Embodiment 1 | ?N 2 | ?250 | ?240 | ?214 | ?83.7 |
| Embodiment 2 | ?Ar | ?250 | ?240 | ?216 | ?84.2 |
| Embodiment 3 | ?N 2 | ?350 | ?10 | ?217 | ?83.4 |
| Embodiment 4 | ?N 2 | ?300 | ?150 | ?215 | ?83.9 |
| Embodiment 5 | ?N 2 | ?200 | ?300 | ?215 | ?83.7 |
| Embodiment 6 | ?N 2 | ?160 | ?440 | ?214 | ?83.6 |
| Embodiment 7 | ?N 2 | ?350 | ?2 | ?213 | ?83.7 |
| Embodiment 8 | ?N 2 | ?250 | ?40 | ?214 | ?84.2 |
The test of catalyst performance:
Above 9 silver catalyst samples are smashed, respectively get 12～18 order sample 0.65g, place the micro anti-evaluation device, carry out the initial performance test under the condition of discharge ring oxidative ethane 1.35% at air speed 7000/h.Test result is listed in table 1.
Place comparative example, embodiment 1 and embodiment 2 the micro anti-evaluation device in air speed 7000/h, carry out stability test under the condition of discharge ring oxidative ethane 2.4%.The temperature of reaction of each catalyzer in the test process and selectivity and the oxyethane total mass mapping of producing, the result as depicted in figs. 1 and 2.
From table 1, Fig. 1 and Fig. 2 as can be seen, the present invention compares with control sample through the heat treated once more silver catalyst sample of rare gas element, and not only active and selectivity is improved, and active in optionally fall off rate is less.
Claims (29)
1. produce the used silver catalyst of oxyethane by oxidation of ethylene for one kind, by the method preparation that may further comprise the steps:
1) usefulness contains the solution impregnation porous heat-resistant carrier of silver compound, organic amine and the various auxiliary agents of q.s;
2) elimination steeping fluid, dry impregnated carrier;
3) being not more than in 21% the nitrogen oxygen atmosphere step 2 in air or oxygen level) the gained carrier carries out primary activation;
4) directly or after cooling, the product of step 3) is heat-treated, make described silver catalyst with rare gas element.
2. silver catalyst as claimed in claim 1, wherein the porous heat-resistant carrier is to contain the porous alumina carrier of Alpha-alumina more than 90%, and has added fusing assistant, carbonaceous material, binding agent and fluoride-mineralization agent in the preparation process of described porous alumina carrier.
3. silver catalyst as claimed in claim 2, wherein said fusing assistant are the magnesium compounds that is selected from magnesium oxide, sal epsom, magnesium nitrate and magnesiumcarbonate, when its add-on is described preparing carriers 0.01%～2.0% of the mixing material gross weight.
4. silver catalyst as claimed in claim 2, wherein said carbonaceous material are refinery coke, carbon dust, graphite, rosin, polyethylene, polypropylene or its mixture, when its consumption is described preparing carriers 5%～30% of the mixing material gross weight.
5. silver catalyst as claimed in claim 2, wherein said fluoride-mineralization agent is one or more the mixture in hydrogen fluoride, aluminum fluoride, Neutral ammonium fluoride, magnesium fluoride, the sodium aluminum fluoride, when its add-on is described preparing carriers 0.01%～2.0% of the mixing material gross weight.
6. silver catalyst as claimed in claim 2, wherein said binding agent are acid or aluminium colloidal sol, the 25-59% of mixing material gross weight when its consumption is described preparing carriers.
7. silver catalyst as claimed in claim 6, wherein said acid are salpeter solution, and wherein the weight ratio of nitric acid and water is 1: 1.25～10.
8. silver catalyst as claimed in claim 2, wherein said porous alumina carrier forms through high-temperature roasting, and maturing temperature is 1250 ℃～1550 ℃.
9. silver catalyst as claimed in claim 2, wherein said porous alumina carrier has following feature: specific surface is 0.1m
2/ g～2.0m
2/ g, pore volume are 0.3～1.0ml/g, water-intake rate 〉=40%, and crushing strength is 20N/ grain～120N/ grain.
10. silver catalyst as claimed in claim 9, wherein said porous alumina carrier has following feature: specific surface is 0.5m
2/ g～1.4m
2/ g, pore volume are 0.5～0.8ml/g, water-intake rate 〉=60%, and crushing strength is 40N/ grain～80N/ grain.
11. silver catalyst as claimed in claim 1, wherein silver compound is silver suboxide, Silver Nitrate or silver oxalate.
12. silver catalyst as claimed in claim 1, wherein should to make the content of silver in described silver catalyst be 1%～30% to the add-on of silver compound, based on the gross weight of described silver catalyst.
13. silver catalyst as claimed in claim 12, wherein the content of silver in described silver catalyst is 5%～25%, based on the gross weight of described silver catalyst.
14. silver catalyst as claimed in claim 1, wherein said auxiliary agent are alkali metal compound and/or alkaline earth metal compound.
15. silver catalyst as claimed in claim 14, wherein said basic metal are selected from lithium, sodium, potassium, rubidium, caesium and any two kinds combination thereof.
16. silver catalyst as claimed in claim 15, wherein said basic metal are caesium.
17. it is 100ppm～1000ppm that silver catalyst as claimed in claim 15, wherein said alkali-metal add-on should make the content of described basic metal in described silver catalyst, based on the gross weight of described silver catalyst.
18. silver catalyst as claimed in claim 14, wherein said alkaline-earth metal is selected from calcium, strontium and barium.
19. silver catalyst as claimed in claim 18, wherein said alkaline-earth metal are barium.
20. it is 50ppm～1000ppm that silver catalyst as claimed in claim 18, the add-on of wherein said alkaline-earth metal should make the content of described alkaline-earth metal in described silver catalyst, based on the gross weight of described silver catalyst.
21. silver catalyst as claimed in claim 14, wherein said auxiliary agent before dipping silver, simultaneously or be applied on the carrier afterwards, or after silver compound is reduced, be immersed on the carrier.
22. silver catalyst as claimed in claim 1, the temperature of wherein said reactivation process are controlled between 200 ℃～700 ℃.
23. silver catalyst as claimed in claim 22, the temperature of wherein said reactivation process are controlled between 200 ℃～500 ℃.
24. silver catalyst as claimed in claim 1, the time of wherein said reactivation process is 1 minute～120 minutes.
25. silver catalyst as claimed in claim 24, the time of wherein said reactivation process is 1 minute～60 minutes.
26. silver catalyst as claimed in claim 1, wherein said heat treatment process is carried out in pure inert gas.
27. silver catalyst as claimed in claim 26, wherein said rare gas element are nitrogen, helium or argon.
28. silver catalyst as claimed in claim 1, the temperature of wherein said heat treatment process are that 150～350 ℃ and time are 1 minute～480 minutes.
29. a method of producing oxyethane by oxidation of ethylene is wherein used as each described silver catalyst in the claim 1～28.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011443448A CN1162416C (en) | 2001-12-17 | 2001-12-17 | Silver catalyst for epoxyethane production, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011443448A CN1162416C (en) | 2001-12-17 | 2001-12-17 | Silver catalyst for epoxyethane production, its preparation method and application |
Publications (2)
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|---|---|
| CN1426835A CN1426835A (en) | 2003-07-02 |
| CN1162416C true CN1162416C (en) | 2004-08-18 |
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| WO2004101144A1 (en) | 2003-05-07 | 2004-11-25 | Shell Internationale Research Maatschappij B.V., | Silver-containing catalysts, the manufacture of such silver containing catalysts, and the use thereof |
| CN103547365B (en) | 2011-04-11 | 2016-03-16 | 陶氏技术投资有限责任公司 | Regulate the method for efficient epoxyethane catalyst |
| CN103721712B (en) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of ethylene produces oxirane silver catalyst |
| CN106693966A (en) * | 2016-11-14 | 2017-05-24 | 中国海洋石油总公司 | Efficient silver catalyst with regular grain size distribution for epoxyethane preparation and preparation method thereof |
| CN111013614B (en) * | 2019-11-06 | 2023-01-13 | 浙江师范大学 | Catalyst carrier and catalyst for preparing chlorine by oxidizing hydrogen chloride, and preparation method and application thereof |
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