CN115069245A - Silver catalyst for producing ethylene oxide by ethylene oxidation and preparation method and application thereof - Google Patents
Silver catalyst for producing ethylene oxide by ethylene oxidation and preparation method and application thereof Download PDFInfo
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- CN115069245A CN115069245A CN202110277385.6A CN202110277385A CN115069245A CN 115069245 A CN115069245 A CN 115069245A CN 202110277385 A CN202110277385 A CN 202110277385A CN 115069245 A CN115069245 A CN 115069245A
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- Prior art keywords
- atmosphere
- silver
- silver catalyst
- gas
- ethylene oxide
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 98
- 239000004332 silver Substances 0.000 title claims abstract description 98
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000005977 Ethylene Substances 0.000 title claims abstract description 31
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims description 13
- 238000007254 oxidation reaction Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003213 activating effect Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 24
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 23
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 40
- 239000011261 inert gas Substances 0.000 claims description 21
- 238000005470 impregnation Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229940100890 silver compound Drugs 0.000 claims description 7
- 150000003379 silver compounds Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910017840 NH 3 Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 34
- 238000001994 activation Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000001569 carbon dioxide Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 10
- -1 silver ions Chemical class 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 150000001553 barium compounds Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 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 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of industrial catalysts, and relates to a silver catalyst for producing ethylene oxide by oxidizing ethylene, and a preparation method and application thereof. The silver catalyst for producing ethylene oxide by oxidizing ethylene comprises the following components: a porous alumina support and silver supported on said porous alumina support, and optionally one or more of the components of a coagent of an alkali metal, an alkaline earth metal, rhenium, and rhenium; the silver catalyst is prepared by adopting a method comprising the following steps: a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture; b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase; c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst; the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere. The silver catalyst of the present invention has significantly improved activity and stability.
Description
Technical Field
The invention belongs to the field of industrial catalysts, and particularly relates to a silver catalyst for producing ethylene oxide by oxidizing ethylene, a preparation method of the silver catalyst for producing ethylene oxide by oxidizing ethylene, and application of the silver catalyst for producing ethylene oxide by oxidizing ethylene.
Background
Under the action of silver catalyst, ethylene is oxidized to produce ethylene oxide and side reaction to produce carbon dioxide, water, etc. with activity, selectivity and stability as the main performance indexes of silver catalyst. The activity is the reaction temperature required for the ethylene oxide production process to reach a certain reaction load, and the lower the reaction temperature, the higher the activity of the catalyst. By selectivity is meant the ratio of the moles of ethylene converted to ethylene oxide in the reaction to the total moles of ethylene reacted. The stability is expressed as the rate of decrease in activity and selectivity, and the smaller the rate of decrease, the better the stability of the catalyst. The silver catalyst with high activity, high selectivity and good stability is used in the process of producing ethylene oxide by oxidizing ethylene, so that the economic benefit can be greatly improved, and the preparation of the silver catalyst with high activity, high selectivity and good stability is the main direction of research on the silver catalyst. The performance of the silver catalyst is not only important in relation to the composition of the catalyst and the preparation method, but also important in relation to the performance of the carrier used in the catalyst and the preparation method.
The preparation method of the silver catalyst mainly comprises two processes of preparing a porous carrier (such as alumina) and applying an active component and an auxiliary agent to the carrier.
The carrier needs to provide a certain surface loaded active component, the active component is uniformly dispersed on the carrier, the silver catalyst generally adopts alpha-alumina as the carrier, and the preparation method mainly comprises the following steps: adding a binder, various additives and the like into the alumina powder raw material, mixing and kneading uniformly, then extruding and molding to form green bodies (Raschig rings, spherical particles, porous columns, saddles and the like) with different shapes, and finally sintering at high temperature to prepare the porous heat-resistant alpha-alumina carrier product, as described in US 5063195A, US 5703001A, US 5801259A and the like. In the preparation process of silver catalyst carrier, auxiliary agent is often added to improve the carrier performance, for example, US5100859A proposes adding alkaline earth metal and SiO in alumina carrier 2 And zirconia, can improve the performance of the silver catalyst.
The application of the active ingredient and the auxiliaries to the support is generally carried out industrially by impregnation activation. Firstly, silver salt, various auxiliary agents and organic amine are prepared into silver-ammonia impregnation solution with a certain concentration, and Ag ions and the organic amine are subjected to a complex reaction to generate silver-organic ammonia complex ions; then the carrier is put into the dipping solution for dipping for enough time, so that the silver-ammonia complex ions and various auxiliary agent ions are dipped on the surface of the carrier along with the solution; after leaching, the carrier is finally put into an activation belt and activated by hot air (or special atmosphere), during the activation process, various silver-containing impregnation components on the surface of the carrier are heated and gradually decomposed, silver ions are reduced into simple substance silver, and particles of tens of nanometers to hundreds of nanometers are formed on the surface of the carrier, so that the finished product silver catalyst is obtained.
Because the final silver particles are generated along with the activation heating process and are limited by various conditions such as activation temperature, atmosphere and the like, the uniformity of the size of the silver particles on the surface of the carrier and the uniformity of distribution are influenced to a certain extent. Thus, the conventional impregnation activation process for industrially preparing a silver catalyst has a limited improvement in the activity and selectivity of the catalyst. In addition, in the industrial application of the silver catalyst, the silver particles on the surface of the carrier can gradually migrate and grow, so that the activity, stability, service life and other properties of the catalyst are affected, the migration and growth of the silver particles are slowed down, and the properties, particularly the stability, of the silver catalyst can also be improved.
Disclosure of Invention
In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies in the field of silver catalysts and processes for preparing the same, and as a result, have found that, after a carrier is immersed in an immersion liquid for a sufficient period of time and filtered and dried, a semi-finished product is obtained in which silver ammine complex ions and various auxiliary ions are carried on the surface of the carrier, and the semi-finished product is brought into sufficient contact with a heated active atmosphere under vacuum conditions or pressurized conditions, to obtain a final finished silver catalyst product having significantly improved activity and stability.
The first aspect of the invention provides a silver catalyst for producing ethylene oxide by oxidizing ethylene, which comprises the following components:
i. a porous alumina support; and
silver supported on said porous alumina support, and optionally one or more components of a co-promoter of an alkali metal, an alkaline earth metal, rhenium, and rhenium;
the silver catalyst is prepared by a method comprising the following steps:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is that the pressure is higher than 1.5 standard atmospheric pressures.
A second aspect of the present invention provides a method for preparing the above silver catalyst, comprising the steps of:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is a pressure higher than 1.5 standard atmospheric pressures.
A third aspect of the invention provides the use of the silver catalyst described above in the epoxidation of ethylene to ethylene oxide.
The silver catalyst provided by the invention has stable performance and higher activity and selectivity, and is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a silver catalyst for producing ethylene oxide by oxidizing ethylene, which comprises the following components:
i. a porous alumina support; and
silver supported on said porous alumina support, and optionally one or more components of a co-promoter of an alkali metal, an alkaline earth metal, rhenium, and rhenium;
the silver catalyst is prepared by adopting a method comprising the following steps:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase (the catalyst semi-finished product) obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is a pressure higher than 1.5 standard atmospheric pressures.
According to the invention, in step c, the inert atmosphere is an atmosphere formed by an inert gas; the weak oxidizing atmosphere is formed by oxidizing gas and inert gas, and the content of the oxidizing gas is lower than 20 v%; the reducing atmosphere is an atmosphere formed by reducing gas or an atmosphere formed by reducing gas and inert gas.
The inert gas, oxidizing gas, or reducing gas may be conventionally selected in the art. In particular, the amount of the solvent to be used,
the inert gas is selected from nitrogen and CO 2 One or more of gaseous alkanes (e.g. methane, ethane, propane, butane) and inert gases of group VIIIA of the periodic Table of elements (e.g. helium, neon), preferably selected from nitrogen, helium and CO 2 Further preferably nitrogen gas.
The oxidizing gas can be selected from one or more of C, H, O, N four elements, preferably oxygen, ozone, and H 2 O 2 Can be, for example, oxygen, ozone, H 2 O 2 The gas mixture with air is more preferably oxygen and/or air.
The reducing gas can be selected from gases with reducibility consisting of C, H, O, N one or more of four elements, preferably selected from hydrogen, CO, NH 3 One or more of gaseous alkene (such as ethylene, propylene and 1-butene) and gaseous alkyne (such as acetylene, propyne and 1-butyne), preferably hydrogen, CO and NH 3 And ethyleneAnd (4) seed preparation.
The atmosphere formed by the oxidizing gas and the inert gas is, for example, oxygen, air, ozone, H 2 O 2 With nitrogen and CO 2 A gaseous alkane and an inert gas of group VIIIA of the periodic Table of the elements.
The atmosphere formed by the reducing gas and the inert gas is, for example, hydrogen, CO, NH 3 One or more of gas olefin and gas alkyne, nitrogen and CO 2 A gaseous alkane and an inert gas of group VIIIA of the periodic Table of the elements.
The amount of the gas to be used is preferably 0.5 to 20% by volume in the oxidizing atmosphere formed by the oxidizing gas and the inert gas.
In the reducing atmosphere formed by the reducing gas and the inert gas, the content of the reducing gas may be higher than 0.5 v%, preferably higher than 1 v%, and more preferably 5 v% to 25 v%.
Before the mixed gas is contacted with the catalyst semi-finished product, the gas components are required to be fully and uniformly mixed.
According to a specific embodiment of the present invention, the activated atmosphere further comprises 0.5 v% to 5 v% of H 2 O。
According to the invention, in the step c, the heating is preferably performed by heating the activating atmosphere to 180-500 ℃, preferably 200-400 ℃.
According to the present invention, in step c, preferably, the solid phase after drying is contacted with the heated activated atmosphere for more than 30 seconds, preferably for 1to 30 minutes.
According to the present invention, the dried solid phase can be activated under vacuum conditions, specifically, the vacuum conditions are preferably a pressure of less than 10Torr, more preferably a pressure of less than 5Torr, and still more preferably a pressure of less than 1 Torr. The dried solid phase may be activated under a pressure condition, specifically, the pressure condition is preferably 0.15MPa to 5MPa, preferably 0.5MPa to 2.5 MPa.
According to one embodiment of the invention, in step c, the dried semi-finished catalyst in solid phase is subjected to a reduction treatment with H 2 Activating under pressure in nitrogen. For example, the reducing gas includes: 5% of H 2 The balance being N 2 The pressure can be selected to be 1.5MPa, the temperature is selected to be 200-400 ℃, and the activation time at least exceeds 30 seconds, preferably 1-30 minutes.
According to a particular embodiment of the invention, the impregnation solution comprises, in addition to the silver compound, optionally at least one selected from the group consisting of alkali metal promoters, alkaline earth metal promoters and rhenium synergists.
According to the invention, preferably, the porous alumina support has the following characteristics: alpha-A1 2 O 3 Content (wt.)>85%, preferably alpha-A1 2 O 3 Content (wt.)>90 percent; particle crush strength>20N, preferably the particle crushing strength is 30-150N; the specific surface area is 0.2 to 7.0m 2 A preferred specific surface area is 0.5 to 6.0 m/g 2 Water absorption per gram>30%, preferably Water absorption>40%, and the pore volume is 0.35-0.85 ml/g, preferably 0.40-0.8 ml/g.
According to the method of the present invention, the silver element contained in the impregnation fluid is derived from a silver compound, which may be any silver compound suitable for preparing a silver catalyst for ethylene oxide production. Silver oxide, silver nitrate and/or silver oxalate are preferably used in the present invention. According to the present invention, the impregnation liquid generally contains an organic amine compound, and the organic amine compound used may be any organic amine compound suitable for preparing a silver catalyst as long as the organic amine compound can form a silver-amine complex with a silver compound. For the purposes of the present invention, preference is given to using pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine or mixtures thereof, for example mixtures of ethylenediamine and ethanolamine.
According to the invention, the alkali metal promoter may be a compound of lithium, sodium, potassium, rubidium or caesium (such as nitrate, sulphate and hydroxide) or a mixture thereof, preferably caesium nitrate, lithium nitrate and/or potassium hydroxide. The alkaline earth metal promoter may be one or more of magnesium, calcium, strontium and barium compounds, such as one or more of oxides, oxalates, sulfates, acetates and nitrates of the alkaline earth metal elements, preferably barium compounds and/or strontium compounds, such as barium acetate and/or strontium acetate.
According to the invention, the rhenium promoter may be an oxide, perrhenic acid, perrhenate, or mixtures thereof, preferably perrhenic acid and/or perrhenate, such as, for example, perrhenic acid, cesium perrhenate and/or ammonium perrhenate, and the like. In addition to the silver compound, the organic amine, the optional alkali metal promoter, the optional alkaline earth metal promoter and the optional rhenium promoter, a co-promoter for the rhenium promoter may be added to the impregnation solution to further improve the activity, selectivity and stability of the resulting silver catalyst. The co-adjuvant of the rhenium adjuvant in the present invention may be one or more selected from the group consisting of chromium compounds, molybdenum compounds, tungsten compounds and boron compounds.
According to a specific embodiment of the present invention, the method comprises the steps of: a. impregnating an alumina support with a solution containing a sufficient amount of a silver compound, an organic amine, an optional alkali metal promoter, an optional alkaline earth metal promoter, and an optional rhenium promoter and a rhenium synergist; b. leaching the impregnation liquid; and c, activating the solid phase obtained after drying in the step b in a reducing atmosphere to prepare the silver catalyst.
According to one embodiment of the invention, an aqueous solution of silver nitrate is first reacted with an aqueous solution of ammonium oxalate or oxalic acid to precipitate a silver oxalate precipitate, which is then filtered, washed with deionized water until free of nitrate ions and dried to obtain an oxalate compound. Then dissolving silver oxalate into the aqueous solution of organic amine such as pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine or their mixture, adding various additives (if necessary) to prepare dipping solution; then, the porous alpha-alumina carrier is impregnated by the obtained impregnation solution under the condition that the vacuum degree is less than 10mmHg for 10to 60 minutes, and then the porous alpha-alumina carrier is drained and dried, wherein the drying temperature can be between room temperature and 100 ℃, and the drying time can be 1to 96 hours; finally, the solution is 5% of H 2 The temperature of the nitrogen gas is kept for 1to 30 minutes within the range of 200 to 400 ℃ for activation.Silver oxide can also be used to replace silver nitrate, and silver oxalate can also be directly complexed with organic amine without leaching and then used to impregnate the carrier.
The silver catalyst of the present invention comprises: a carrier, silver, optionally an alkali metal, optionally an alkaline earth metal, optionally rhenium, and optionally a rhenium co-promoter element. According to the present invention, the optional means may or may not include, such as optional alkali metal, means that the catalyst may or may not include alkali metal.
In a specific embodiment of the above silver catalyst, the alkali metal is one or more selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium; preferably cesium and/or potassium, most preferably cesium. The alkaline earth metal is one or more selected from magnesium, calcium, strontium and barium, preferably strontium and/or barium. The rhenium co-promoter element is selected from at least one of chromium, molybdenum, tungsten and boron.
According to the silver catalyst of the present invention, silver is dispersed on the surface and in the pores of the alumina support. In order to control the economy on the basis of ensuring the catalyst performance, the content of silver is 1-35 wt%, preferably 5-30 wt%, based on the total weight of the silver catalyst; the content of the alkali metal is 5-2000 ppm, preferably 10-1500 ppm; the content of rhenium is 5-1500 ppm, preferably 10-1000 ppm; the content of the synergistic auxiliary element of rhenium is 5-1000 ppm, preferably 10-500 ppm.
The invention also provides a preparation method of the silver catalyst, which comprises the following steps:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is a pressure higher than 1.5 standard atmospheric pressures.
The materials and process conditions used in the preparation method are consistent with the above definitions and are not described herein again.
The invention also provides the application of the silver catalyst in the production of ethylene oxide by ethylene oxidation.
The method provided by the invention is simple and easy to implement, the obtained silver catalyst has proper or higher catalytic activity, and the stability of the obtained silver catalyst is obviously improved, so that the method is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Determination of catalyst Performance: various silver catalysts of the present invention were tested for their activity and selectivity using a laboratory microreactor (hereinafter referred to as "microreaction") evaluation apparatus. The reactor used in the microreaction evaluation device was a stainless steel reaction tube having an inner diameter of 4mm, and the reaction tube was placed in a heating mantle. The filling volume of the catalyst is 1ml, and the lower part of the catalyst is provided with inert filler, so that a catalyst bed layer is positioned in a constant temperature area of the heating sleeve.
The conditions for determining the activity and selectivity employed in the present invention are as follows: composition of reaction gas, ethylene (C) 2 H 4 ) 28.0 +/-1.0 mol%; oxygen (O) 2 ) 7.4 +/-0.2 mol%; carbon dioxide (CO) 2 ) < 5.0 mol%; cause steady qi (N) 2 ) And the rest; 0.1-2.0ppm of inhibitor dichloroethane; the space velocity is 8000/h; the reactor outlet EO concentration, 3.0 mol%; space-time yield, 470kg EO/m 3 Cat./h。
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The selectivity was calculated after volume shrinkage correction of the measurement results according to the following formula:
selectivity is selected
Where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO 2 Is a reactionThe carbon dioxide concentration difference between the outlet gas and the inlet gas of the device is taken as the average of more than 10 groups of test data to be used as the test result of the day.
Preparation of Carrier A
300g of 50-500 mesh trihydrate A1 2 O 3 And 150g of pseudo-monohydrate A1 sieved with a 200 mesh sieve 2 O 3 The mixture is put into a mixer to be mixed evenly, and then is transferred into a kneader, 100 ml of 20 weight percent nitric acid aqueous solution is added, and the mixture is kneaded into paste which can be extruded and molded. Extrusion molding into a single-hole Raschig ring column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 2.0mm, and drying at 80-120 deg.C for 2 hr to reduce the free water content to below 10 wt% to obtain a green body. Then placing the green body into an electric furnace, raising the temperature from room temperature to 1200-1500 ℃ for 30 hours, and keeping the temperature at the high temperature for 1-6 hours to obtain white alpha-A1 2 O 3 Vector A, alpha-A1 2 O 3 Content (wt.)>90%, crushing strength 140N, specific surface area 1.1m 2 Water absorption of 50% and pore volume of 0.5 ml/g.
Comparative example 1
In a glass flask with a stirrer, 3.75g of ethylenediamine, 1.38g of ethanolamine and 4.75g of deionized water were added to obtain a mixed solution. And slowly adding the silver oxalate into the obtained mixed solution under stirring, keeping the temperature at 15-35 ℃, completely dissolving the silver oxalate, and adding the silver oxalate in an amount which ensures that the finally prepared impregnation solution contains 24 wt% of silver. Adding 0.04g of cesium nitrate and 0.05g of ammonium perrhenate, and adding deionized water to make the total mass of the solution reach 25g to prepare impregnation liquid for later use. 10g of the carrier A was taken and placed in a vacuum vessel. Vacuumizing to a vacuum degree lower than 10mmHg, adding the above impregnation liquid, immersing the carrier, and keeping for 30 minutes. After which the excess impregnation solution is leached away. And heating the impregnated carrier in an open-environment normal-pressure air flow at 250 ℃ for 5 minutes, and cooling to obtain the silver catalyst.
Example 1
In a glass flask with stirring, 3.75g of ethylenediamine, 1.38g of ethanolamine and 4.75g of deionized water were added to obtain a mixed solution. Slowly adding silver oxalate into the obtained mixed solution with stirring, keeping the temperature at 15-35 ℃,the silver oxalate was completely dissolved, and the amount of silver oxalate added was such that the finally obtained impregnation solution contained 24 wt% silver. Adding 0.04g of cesium nitrate and 0.05g of ammonium perrhenate, and adding deionized water to make the total mass of the solution reach 25g to prepare impregnation liquid for later use. 10g of the carrier A was taken and placed in a vacuum vessel. Vacuumizing to a vacuum degree lower than 10mmHg, adding the above impregnation liquid, immersing the carrier, and keeping for 30 minutes. After which the excess impregnation solution is leached away. Pressurizing the impregnated carrier to 1.5MPa in an activating atmosphere at 250 ℃, heating for 5 minutes, and cooling to obtain the silver catalyst S1, wherein the activating atmosphere is a reducing atmosphere and contains 5 v% of H 2 The balance being N 2 。
Example 2
The procedure was as in example 1, except that the activating atmosphere was a reducing atmosphere containing 1 v% of H 2 The balance being N 2 。
Example 3
The procedure was as in example 1, except that the activating atmosphere was a reducing atmosphere containing 20 v% H 2 The balance being N 2 。
Example 4
The procedure was as in example 1, except that the activating atmosphere was a reducing atmosphere containing 5% CO, the remainder being CO 2 。
Example 5
The procedure is as in example 1, except that the activating atmosphere is an inert gas N 2 。
Example 6
The procedure is as in example 1, except that the activating atmosphere is an inert gas CO 2 。
Example 7
The procedure is as in example 1, except that the activating atmosphere is an inert atmosphere containing 50% by volume of CO 2 And 50 v% of N 2 。
Example 8
The procedure was as in example 1, except that the activating atmosphere was an oxidizing atmosphere containing 5 v% of O 2 The balance being N 2 。
Example 9
The procedure was as in example 1, except that the activating atmosphere was an oxidizing atmosphere containing 1 v% of O 2 The balance being N 2 。
Example 10
The procedure was as in example 1, except that the activating atmosphere was an oxidizing atmosphere containing 15% by volume of O 2 The balance being N 2 。
Example 11
The procedure is as in example 1, except that the activating atmosphere is an oxidizing atmosphere containing 1% O 2 The balance being N 2 。
Example 12
The procedure is as in example 1, except that the activating atmosphere is an oxidizing atmosphere containing 5% of O 2 1% of H 2 O 2 The balance being N 2 。
Example 13
The procedure was as in example 1, except that the activating atmosphere was a reducing atmosphere containing 5% CO and 1% H 2 1% of H 2 O and the balance of nitrogen.
Example 14
The procedure was the same as in example 1, except that the activation was carried out under reduced pressure of 9 Torr.
Example 15
The procedure was as in example 6, except that the activation was carried out under reduced pressure of 9 Torr.
Example 16
The procedure was as in example 9, except that the activation was carried out under reduced pressure of 1 Torr.
Test example
Performance evaluation: the activity and selectivity of each catalyst sample was determined using a microreactor evaluation unit under the process conditions described in the "determination of catalyst Performance" section above and the results of the tests are set forth in Table 1. The reaction temperatures in Table 1 are such that the cumulative EO production amounts to 200T/M 3 The value at the time of the catalyst,selectively taking the cumulative EO yield to 200T/M 3 Average value in catalyst.
TABLE 1
As can be seen from table 1, the silver catalyst treated under the special atmosphere and the pressure or pressure reducing conditions has better catalytic activity than the silver catalyst treated by the traditional activation treatment, and the stability and selectivity of the obtained silver catalyst are obviously improved, so that the silver catalyst is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
It can be seen that the silver catalyst obtained by adopting the heated inert, oxidizing and reducing gases to fully contact and heat and activate under the vacuum condition or the pressurizing condition can obtain obviously improved activity, stability and selectivity when being used for catalyzing the oxidation of ethylene to prepare ethylene oxide.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Claims (11)
1. A silver catalyst for ethylene oxidation to produce ethylene oxide comprises the following components:
i. a porous alumina support; and
silver supported on said porous alumina support, and optionally one or more components of a co-promoter of an alkali metal, an alkaline earth metal, rhenium, and rhenium;
the silver catalyst is prepared by adopting a method comprising the following steps:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is a pressure higher than 1.5 standard atmospheric pressures.
2. The silver catalyst for ethylene oxidation to ethylene oxide according to claim 1, wherein, in the step c,
the inert atmosphere is formed by inert gas;
the weak oxidizing atmosphere is formed by oxidizing gas and inert gas, and the content of the oxidizing gas is lower than 20 v%;
the reducing atmosphere is formed by reducing gas or formed by reducing gas and inert gas;
the inert gas is selected from nitrogen and CO 2 One or more of gaseous alkanes and inert gases of group VIIIA of the periodic Table of the elements, preferably selected from nitrogen, helium and CO 2 Further preferably nitrogen gas;
the oxidizing gas is selected from C, H, O, N one or more of four elements with oxidizing property, preferably oxygen, ozone, and H 2 O 2 One or more of;
the reducing gas is selected from C, H, O, N containing one or more of four elementsThe reducing gas is preferably selected from hydrogen, CO, NH 3 One or more of gaseous olefins and gaseous alkynes, more preferably hydrogen, CO, NH 3 And ethylene.
3. The silver catalyst for ethylene oxidation to ethylene oxide according to claim 2, wherein the content of the oxidizing gas in the oxidizing atmosphere formed by the oxidizing gas and the inert gas is between 0.5 v% and 20 v%;
in the reducing atmosphere formed by the reducing gas and the inert gas, the content of the reducing gas is more than 0.5 v%, preferably the content of the reducing gas is more than 1 v%, and more preferably the content of the reducing gas is 5 v% to 25 v%.
4. The silver catalyst for ethylene oxidation to ethylene oxide according to claim 1, wherein the activating atmosphere further comprises 0.5 to 5% by volume of H 2 O。
5. The silver catalyst for ethylene oxidation to ethylene oxide according to any one of claims 1to 4, wherein, in step c,
the heating is to heat the activated atmosphere to 180-500 ℃, preferably 200-400 ℃;
the sufficient contact is to contact the dried solid phase with the heated activated atmosphere for more than 30 seconds, preferably for 1to 30 minutes.
6. The silver catalyst for ethylene oxidation to ethylene oxide according to any one of claims 1to 4, wherein, in step c,
the vacuum condition is a pressure of less than 10Torr, preferably a pressure of less than 5Torr, more preferably a pressure of less than 1 Torr;
the pressurizing condition is a pressure of 0.15MPa to 5MPa, preferably 0.5MPa to 2.5 MPa.
7. The silver catalyst for ethylene oxidation to ethylene oxide according to any one of claims 1to 4, wherein the impregnation fluid comprises a silver compound and optionally at least one selected from the group consisting of an alkali metal promoter, an alkaline earth metal promoter and a rhenium co-promoter.
8. The silver catalyst for ethylene oxidation to ethylene oxide according to any one of claims 1to 4, wherein the porous alumina support has the following characteristics: alpha-A1 2 O 3 Content (c) of>85%, preferably alpha-A1 2 O 3 Content (wt.)>90 percent; particle crush strength>20N, preferably the particle crushing strength is 30-150N; the specific surface area is 0.2 to 7.0m 2 A preferred specific surface area is 0.5 to 6.0 m/g 2 Water absorption per gram>30%, preferably Water absorption>40%, and the pore volume is 0.35-0.85 ml/g, preferably 0.40-0.8 ml/g.
9. The silver catalyst for ethylene oxidation to ethylene oxide according to any one of claims 1to 4, wherein the silver is contained in an amount of 1to 35 wt%, preferably 5to 30 wt%, based on the total weight of the silver catalyst; the content of the alkali metal is 5-2000 ppm, preferably 10-1500 ppm; the content of rhenium is 5-1500 ppm, preferably 10-1000 ppm; the content of the synergistic auxiliary element of rhenium is 5-1000 ppm, preferably 10-500 ppm.
10. The method for preparing a silver catalyst according to any one of claims 1to 9, comprising the steps of:
a. impregnating the porous alumina carrier with a silver-containing impregnating solution to obtain a solid-liquid mixture;
b. b, performing solid-liquid separation on the solid-liquid mixture obtained in the step a, and drying the obtained solid phase;
c. under the vacuum condition or the pressurization condition, fully contacting the dried solid phase obtained in the step b with a heated activation atmosphere for activation to obtain the silver catalyst;
the activating atmosphere is inert atmosphere, weak oxidizing atmosphere or reducing atmosphere;
the vacuum condition is that the pressure is less than 20 Torr; the pressurization condition is a pressure higher than 1.5 standard atmospheric pressures.
11. Use of a silver catalyst according to any one of claims 1to 9 in the epoxidation of ethylene to ethylene oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116474769A (en) * | 2023-04-06 | 2023-07-25 | 武汉工程大学 | Method for improving catalyst activity of ethylene epoxidation reaction system by induction of reaction gas |
| WO2023159315A1 (en) * | 2022-02-25 | 2023-08-31 | University Of Saskatchewan | Method for the preparation of alkene oxides using ozone at room temperature |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762584A (en) * | 2005-09-09 | 2006-04-26 | 天津大学 | Monolithic supported silver catalyst and its preparation method and its use in ethylene epoxidation reaction |
| WO2006111600A1 (en) * | 2005-04-19 | 2006-10-26 | Consejo Superior De Investigaciones Científicas | Method and catalysts for the epoxidation of olefinic compounds in the presence of oxygen |
| JP2009179580A (en) * | 2008-01-30 | 2009-08-13 | Sumitomo Chemical Co Ltd | Process for producing olefin oxide |
| CN102333767A (en) * | 2009-12-28 | 2012-01-25 | 陶氏技术投资有限公司 | Method of controlling the production of silver chloride on a silver catalyst in the production of alkylene oxides |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method thereof, silver catalyst prepared from carrier and application of silver catalyst |
| CN111905731A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Method for activating silver catalyst |
| CN111905732A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Silver catalyst and activation method and application thereof |
| WO2021000523A1 (en) * | 2019-07-02 | 2021-01-07 | 中国科学院大连化学物理研究所 | Optimized activation method for polyol hydrogenolysis catalyst |
-
2021
- 2021-03-15 CN CN202110277385.6A patent/CN115069245B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006111600A1 (en) * | 2005-04-19 | 2006-10-26 | Consejo Superior De Investigaciones Científicas | Method and catalysts for the epoxidation of olefinic compounds in the presence of oxygen |
| CN1762584A (en) * | 2005-09-09 | 2006-04-26 | 天津大学 | Monolithic supported silver catalyst and its preparation method and its use in ethylene epoxidation reaction |
| JP2009179580A (en) * | 2008-01-30 | 2009-08-13 | Sumitomo Chemical Co Ltd | Process for producing olefin oxide |
| CN102333767A (en) * | 2009-12-28 | 2012-01-25 | 陶氏技术投资有限公司 | Method of controlling the production of silver chloride on a silver catalyst in the production of alkylene oxides |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method thereof, silver catalyst prepared from carrier and application of silver catalyst |
| CN111905731A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Method for activating silver catalyst |
| CN111905732A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Silver catalyst and activation method and application thereof |
| WO2021000523A1 (en) * | 2019-07-02 | 2021-01-07 | 中国科学院大连化学物理研究所 | Optimized activation method for polyol hydrogenolysis catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023159315A1 (en) * | 2022-02-25 | 2023-08-31 | University Of Saskatchewan | Method for the preparation of alkene oxides using ozone at room temperature |
| CN116474769A (en) * | 2023-04-06 | 2023-07-25 | 武汉工程大学 | Method for improving catalyst activity of ethylene epoxidation reaction system by induction of reaction gas |
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