CN106955693B - Alpha-alumina carrier of silver catalyst for ethylene epoxidation as well as preparation and application thereof - Google Patents
Alpha-alumina carrier of silver catalyst for ethylene epoxidation as well as preparation and application thereof Download PDFInfo
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- CN106955693B CN106955693B CN201610011592.6A CN201610011592A CN106955693B CN 106955693 B CN106955693 B CN 106955693B CN 201610011592 A CN201610011592 A CN 201610011592A CN 106955693 B CN106955693 B CN 106955693B
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- Prior art keywords
- carrier
- alpha
- alumina
- silver catalyst
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 68
- 239000004332 silver Substances 0.000 title claims abstract description 68
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000005977 Ethylene Substances 0.000 title claims abstract description 27
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 40
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 28
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 18
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- -1 amine compound Chemical class 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008247 solid mixture Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- 229940099259 vaseline Drugs 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229940100890 silver compound Drugs 0.000 claims description 7
- 150000003379 silver compounds Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000001050 lubricating effect Effects 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 230000000704 physical effect Effects 0.000 description 15
- 150000004684 trihydrates Chemical class 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000002671 adjuvant Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical group [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical group [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 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
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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Abstract
The invention relates to an alpha-alumina carrier of a silver catalyst for ethylene epoxidation and a preparation method thereof, wherein micron-sized alpha-alumina crystal grains and a silicon-containing auxiliary agent compound are added in a certain proportion in the preparation process of the carrier, so that the prepared alpha-alumina carrier of the silver catalyst has good porosity, specific surface area and pore structure, 40-60 percent (volume) of pores with the pore diameter of 0.5-1.5 mu m in pore distribution and 10-30 percent (volume) of pores with the pore diameter of 5-10 mu m in pore distribution. The invention also relates to a silver catalyst prepared by the alpha-alumina carrier and application thereof in producing ethylene oxide by ethylene epoxidation, wherein the silver catalyst prepared by dipping, drying and activating a composition solution of a silver-containing compound, an organic amine compound, an alkali metal assistant, an alkaline earth metal assistant, a rhenium assistant and an optional rhenium assistant co-assistant is used for preparing ethylene oxide by ethylene epoxidation and has higher activity and selectivity.
Description
Technical Field
The invention belongs to the technical field of catalyst carriers and catalyst preparation, and particularly relates to an alpha-alumina carrier of a silver catalyst for ethylene epoxidation, and preparation and application thereof.
Background
Ethylene epoxidation under the action of a silver catalyst produces mainly Ethylene Oxide (EO) and simultaneously produces carbon dioxide and water as side reactions, wherein activity, selectivity and stability are the main performance indexes of the silver catalyst. The activity refers to the reaction temperature required when the ethylene oxide production process reaches a certain reaction load, and the lower the reaction temperature is, the higher the activity of the catalyst is; selectivity refers to the ratio of moles of ethylene converted to ethylene oxide in the reaction to the total reacted moles of ethylene; stability is expressed as the rate of decline of activity and selectivity, with the lower the rate of decline the better the stability of the catalyst.
Currently, there are three types of silver catalysts: the catalyst has high activity, good stability, initial selectivity of 80-82% and service life of 2-5 years, and is suitable for all ethylene oxide/ethylene glycol (EO/EG) production devices; the second is high-selectivity silver catalyst, the initial selectivity of the catalyst reaches over 88 percent, but the catalyst requires CO in reaction gas at the inlet of the reactor 2 The concentration is below 1.0 percent, and the method is suitable for a newly-built EO/EG production device with relatively low space-time yield; thirdly, the silver catalyst with medium selectivity (the silver catalyst with activity and selectivity between the former two) can reach the selectivity of 83-85 percent, and the CO in the reaction gas at the inlet of the reactor is required to be added 2 The concentration is below 3%. The selectivity of different catalysts can be determined according to CO in the reaction gas 2 The concentration and the EO concentration at the outlet are correspondingly adjusted, and in recent years, the silver catalyst with high selectivity and the silver catalyst with medium selectivity are widely applied to industrial production and replace the original silver catalyst with high activity.
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 by the catalyst and the preparation method. For the reaction with alpha-Al 2 O 3 As for the carrier as the main component, the physical properties of the carrier include compressive strength, porosity, specific surface area, pore distribution and the like, and a good catalyst carrier has excellent compressive strength, porosity and specific surface area. The higher porosity can reduce the diffusion resistance of reactant and product gases under reaction conditions; the specific surface area of the carrier is required to have the minimum value so as to ensure the catalytic component to be capable ofCan be impregnated on the carrier; the compressive strength is a parameter that measures the physical integrity of the support and is necessary to ensure a long service life for the catalyst to withstand the operating conditions. The carrier has better specific surface area and porosity, and the compressive strength can be reduced; conversely, high compressive strength reduces the specific surface area and porosity. The balance between different physical properties is very important for the carrier.
US5384302 uses two different particle sizes of alpha-Al 2 O 3 And trihydrate and monohydrate alumina are used as raw materials, a titanium-containing auxiliary agent, a pore-forming agent, a ceramic binder and the like are added to prepare a carrier, and the carrier has better compressive strength and porosity after being calcined at 1500 ℃, so that the catalyst prepared from the carrier has better performance.
US7060651 describes a high-silicon carrier containing more than 70% of silicon oxide and having a specific surface area of 0.5-30m 2 The catalyst is prepared by using at least one of metal components of platinum, palladium, silver, molybdenum, titanium, zirconium, copper and the like or oxide thereof as an active component, wherein the content of the active component is not more than 2 percent of the metal content, and the active component is immersed and loaded on a carrier at 40-200 ℃ in a solution form and then is subjected to heat treatment to obtain the catalyst which can be used for ethylene or propylene epoxidation reaction.
Chinese patent CN1217233A describes that the carrier is prepared by calcining three-water alpha-alumina with different particle sizes, pseudo-one-water alumina with a certain proportion, pore-forming agent, fluxing agent, mineralizer, auxiliary agent and the like at the temperature of 1300 ℃ and 1500 ℃, and the catalyst prepared by the carrier has higher selectivity.
Chinese patent CN1634652A describes that no pore-forming agent is added in the preparation process of the carrier, and the carrier is prepared by directly roasting 50-500 mesh alpha-alumina trihydrate, a certain proportion of pseudo-monohydrate alumina, a fluxing agent, a mineralizing agent, an auxiliary agent and the like at the temperature of 1250-.
Chinese patent CN103372466A is prepared by mixing alpha-alumina trihydrate, pseudo-monohydrate alumina, mineralizer, alkaline earth metal compound assistant, and burnable lubricant at different proportions, kneading, extruding, and calcining at high temperature to obtain carrier, wherein the mineralizer can reduce the crystal transition temperature of alumina, the alumina wafers are distributed in a sheet-like cross manner, and the carrier has high strength.
US8791280 describes a method for preparing a low surface area alpha-phase alumina carrier, wherein the content of alpha-phase alumina is more than 90 wt%, the content of silicon is less than 6 wt%, the alpha-phase alumina and/or transition phase alumina, a binder, a solid pore-forming agent and a water-soluble titanium compound are dry-mixed, added with water for extrusion molding, dried and roasted at 1150-1600 ℃ to prepare the carrier, and the pore volume of the carrier is 0.2-0.8ml/g, preferably 0.25-0.6 ml/g; the specific surface area is 0.4-4.0m 2 A/g, more suitably from 0.6 to 1.5 ml/g; the crush strength is greater than 8 pounds, more preferably greater than 10 pounds.
In view of the importance of the balance between the physical properties of the catalyst carrier to the carrier, research and development of an α -alumina carrier for a silver catalyst for ethylene epoxidation with good compressive strength, porosity and specific surface area are urgently needed.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide an α -alumina carrier of a silver catalyst for ethylene epoxidation, which has good compressive strength, porosity and specific surface area. The invention also provides a preparation method of the alpha-alumina carrier, which adds micron-sized alpha-Al in the preparation process of the carrier 2 O 3 The mode of crystal grains reduces alpha-Al 2 O 3 While increasing the specific surface area of the carrier by adding the silicon-containing auxiliary agent. When the silver catalyst prepared by the alpha-alumina carrier is used for preparing ethylene oxide by ethylene epoxidation, the activity and the selectivity of the catalyst can be obviously improved.
To this end, the present invention provides in a first aspect an α -alumina support for a silver catalyst for ethylene epoxidation, obtained by shaping, drying and calcining an α -alumina support precursor mixture, wherein the α -alumina support precursor mixture comprises:
component a, trihydrate alpha-Al with the particle size of 25-300 mu m 2 O 3 ；
Component b, pseudo-monohydrate Al with a particle size of less than 75 μm 2 O 3 ；
Component c, alpha-Al with a particle size of 3-8 μm 2 O 3 ；
Component d, a heavy alkaline earth metal compound;
component e, a silicon-containing auxiliary agent;
component f, a burnable lubricating material;
component g, a binder.
In some embodiments of the invention, the composition of the alpha-alumina support precursor mixture, based on the total weight of solid components a-e, is as follows:
in some preferred embodiments of the invention, the composition of the alpha-alumina support precursor mixture, based on the total weight of the solid components a-e, is as follows:
according to the invention, the heavy alkaline earth metal compound comprises one or more of oxides, sulfates, acetates, nitrates and oxalates of heavy alkaline earth metals; preferably, the heavy alkaline earth metal is strontium and/or barium.
In some embodiments of the invention, the silicon containing adjuvant comprises a silicate and/or a silica.
In other embodiments of the present invention, the burnout lubricant material is selected from one or more of petroleum coke, carbon powder, graphite, and petrolatum.
In other embodiments of the invention, the weight ratio of the binder to water is 1 (1.25-10); the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
According to the invention, the crushing strength of the alpha-alumina carrier is 40-160N/grain; preferably 60-130N/grain; the specific surface area is 0.7-2.5m 2 (ii)/g; preferably 0.9-1.8m 2 (ii)/g; the pore volume is 0.35-0.75 ml/g; preferably 0.45-0.70ml(ii)/g; based on the total pore volume, pores with the pore diameter of 0.5-1.5 μm account for 40-60% (by volume), and pores with the pore diameter of 5-10 μm account for 10-30% (by volume).
In a second aspect, the present invention provides a method for preparing an α -alumina support according to the first aspect of the present invention, which comprises:
step S1, mixing the components a-e to form a solid mixture;
step S2, mixing the component f and the component g with the solid mixture to prepare an alpha-alumina carrier precursor mixture;
and step S3, molding the alpha-alumina carrier precursor mixture, drying and roasting to obtain the alpha-alumina carrier.
In some embodiments of the present invention, in step S3, the temperature of the firing is 1350-.
In a third aspect, the present invention provides a silver catalyst for ethylene epoxidation comprising the following components, based on the total weight of the catalyst:
component i, an α -alumina support as described in the first aspect of the present invention or as prepared by the method of the second aspect of the present invention;
in some preferred embodiments of the present invention, the silver catalyst comprises the following components, based on the total weight of the catalyst:
component i, an alpha-alumina carrier according to the first aspect of the present invention or prepared according to the method of the second aspect of the present invention;
in a fourth aspect, the present invention provides a method for preparing a silver catalyst according to the third aspect, which is obtained by immersing the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared according to the second aspect of the present invention in a solution containing a silver compound, an organic amine compound, and an auxiliary agent, followed by activation heat treatment; the aid comprises an alkali metal aid, an alkaline earth metal aid, a rhenium aid and an optional rhenium aid co-aid.
In a fifth aspect, the present invention provides a process for the epoxidation of ethylene to ethylene oxide, wherein the ethylene is subjected to epoxidation in the presence of a silver catalyst according to the third aspect of the present invention or a silver catalyst prepared by a process according to the fourth aspect of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will now be described in detail with reference to the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
As described above, if the existing silver catalyst carrier has a good specific surface area and porosity, the compressive strength may be reduced; on the contrary, the specific surface area and porosity are reduced when the compressive strength is high. In view of the balance between the physical properties of the catalyst carrier, the inventors of the present invention have conducted extensive and intensive studies in the field of preparation of silver catalyst carriers, and found that micron-sized α -Al is added to α -alumina trihydrate and pseudo-alumina monohydrate as raw materials during the preparation of the carriers 2 O 3 The crystal grains can reduce the crystal transformation of hydrated alumina into alpha-Al 2 O 3 While reducing the calcination temperature of alpha-Al 2 O 3 The crystal size of (a); the specific surface area of the carrier can be increased by adding the silicon-containing auxiliary agent; the silver catalyst carrier prepared by the method has good compressive strength, porosity and specific surface area, and when the silver catalyst prepared by the carrier is used for preparing ethylene oxide by ethylene epoxidation, the activity and selectivity of the catalyst can be obviously improved. The present invention has been made based on the above findings.
The alpha-alumina carrier of the silver catalyst for ethylene epoxidation in the first aspect of the invention is prepared by mixing micron alpha-Al 2 O 3 Crystal grainThe alpha-alumina carrier precursor mixture is prepared by molding, drying and roasting, wherein the mass content of the alpha-alumina is more than 90 percent. The crushing strength of the alpha-alumina carrier is 40-160N/grain; preferably 60-130N/pellet. The specific surface area is 0.7-2.5m 2 (iv) g; preferably 0.9-1.8m 2 (ii) in terms of/g. The pore volume is 0.35-0.75 ml/g; preferably 0.45-0.70 ml/g. Based on the total pore volume, the pores with the pore diameter of 0.5-1.5 μm account for 40-60% (volume), and the pores with the pore diameter of 5-10 μm account for 10-30% (volume).
According to some embodiments of the present invention, the method for preparing an α -alumina support according to the second aspect of the present invention, as defined in the first aspect of the present invention, comprises the steps of:
(1) a solid mixture having the following composition was prepared:
component a, 25-300 μm of alpha-A1 trihydrate in an amount of 30-80% by weight based on the total weight of the solid mixture 2 O 3 ；
Component b, pseudo-monohydrate A1 with a particle size of less than 75 μm in an amount of 10% to 45% by weight, based on the total weight of the solid mixture 2 O 3 ；
Component c, alpha-A1 with a particle size of 3-8 μm in an amount of 1.0% -25% by weight based on the total weight of the solid mixture 2 O 3 ；
Component d, a heavy alkaline earth metal compound in an amount of 0.01% to 2.5% by weight based on the total weight of the solid mixture;
component e, a silicon-containing adjuvant in an amount of 0.01 to 1.0% by weight based on the total weight of the solid mixture.
(2) Adding a combustible lubricating material of the component f into the solid mixture obtained in the step (1), wherein the adding amount is 0.01-5.0 percent of the total weight of the solid mixture;
(3) adding a component g of a binder to the mixture of step (2) to obtain an alpha-alumina support precursor mixture in an amount of 25 to 60 weight percent based on the total weight of the solid mixture;
(4) kneading and extruding the alpha-alumina carrier precursor mixture obtained in the step (3), drying, and roasting at 1350-1480 ℃ to obtain alpha-A1 2 O 3 And (3) a carrier.
In the preparation method of the carrier, the trihydrate alpha-A1 2 O 3 Dehydration and crystal transformation into alpha-A1 in the high-temperature roasting process 2 O 3 (ii) a Pseudo-water A1 2 O 3 Reacting with acid during acid kneading, converting into sol, acting as binder, and converting into stable alpha-A1 during high temperature roasting 2 O 3 To alpha-A1 2 O 3 A portion of a carrier; the micron-sized alpha-A1 2 O 3 Water-free, in the form of particles with a particle size of 3 to 8 μm, preferably added in an amount of 2.0% to 20% by weight, based on the total weight of the solid mixture, of alpha-A1 of micron size 2 O 3 The crystal grains can be used as seed crystals and can reduce the conversion of the hydrated alumina to alpha-A1 2 O 3 And decrease of alpha-A1 2 O 3 The grain size of (a).
In the above-mentioned method for preparing the carrier, the heavy alkaline earth metal is added in an amount of preferably 0.2 to 2.0% by weight based on the total weight of the solid mixture, for the purpose of improving the carrier properties. The heavy alkaline earth metal is preferably strontium and/or barium. Correspondingly, the heavy alkaline earth metal compound is a compound of strontium and/or barium. The strontium and/or barium compound comprises one or more of strontium and/or barium oxide and strontium and/or barium corresponding salt; the salt corresponding to the strontium and/or barium comprises one or more of sulfate, acetate, nitrate and oxalate of the strontium and/or barium.
In the above method for preparing the carrier, the silicon-containing adjuvant comprises silicate and/or silica, etc., and is used for increasing the small pores in the carrier and keeping the specific surface area of the carrier high, and the addition amount is preferably 0.1-0.5 wt% based on the total weight of the solid mixture.
In some embodiments of the present invention, the silicon containing adjuvant is present in the carrier in an amount of 65 to 7500ppm by weight, based on elemental silicon; preferably, the silicon-containing adjuvant is present in the carrier in an amount of 400-4500ppm by weight.
In the preparation method of the carrier, the combustible lubricating material is added to ensure that the kneaded material is easy to form and granulate, meanwhile, oxidation reaction is generated in the roasting process of the material, generated gas escapes, and impurities are not introduced or introduced as little as possible when the carrier is prepared, so that the performance of the catalyst is not influenced. The burnout lubricating material is preferably one or more of petroleum coke, carbon powder, graphite and vaseline, and the addition amount thereof is preferably 0.05-4 wt% based on the total weight of the solid mixture.
In the preparation method of the carrier, a binder solution is added, wherein the weight ratio of the binder to water in the binder solution is 1 (1.25-10); preferably the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid. Binder and pseudo-hydrated Al in the components of the silver catalyst carrier of the invention 2 O 3 Generating aluminum sol, and bonding the components together to form paste which can be extruded and molded. The binder and pseudo-monohydrate Al in the invention 2 O 3 The aluminum sol can be used in full or partial replacement.
The preparation method of the carrier comprises the steps of kneading the solid mixture with a binder to obtain a paste, extruding and molding the paste, and drying the paste until the water content is below 10%, wherein the carrier can be in a ring shape, a spherical shape, a cylindrical shape or a porous cylindrical shape. The drying temperature is preferably 80-120 deg.C, and the drying time is preferably controlled at 1-24h according to the water content.
In some embodiments of the present invention, the calcination time in the step (4) is 1-20 h; preferably, the roasting time is 2-15h, and the roasting makes the alumina completely converted into alpha-A1 2 O 3 。
The silver catalyst for ethylene epoxidation according to the third aspect of the present invention is obtained based on the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared by the method according to the second aspect of the present invention, and contains, in addition to the α -alumina carrier, a metal element in a co-promoter of a silver element, an alkali metal element, an alkaline earth metal element, a rhenium element, and a rhenium promoter.
In some embodiments of the invention, the alkali metal is selected from at least one of lithium, sodium, potassium, rubidium, and cesium.
In other embodiments of the present invention, the alkaline earth metal is selected from at least one of calcium, magnesium, strontium, and barium.
According to some embodiments of the invention, the elemental silver is present in the catalyst in an amount of from 5% to 37% by weight, based on the total weight of the catalyst; preferably from 8% to 32% by weight; the content of alkali metal element is 5-3000ppm (weight); preferably 10 to 2000ppm by weight; the content of the alkaline earth metal element is 500-; preferably 1500-; the content of rhenium metal element is 10-1000ppm (weight); preferably 100-800ppm by weight; the content of the co-promoter of the rhenium promoter is less than or equal to 200ppm (weight) calculated by metal elements in the co-promoter of the rhenium promoter; preferably 5 to 200ppm by weight; more preferably 20 to 150ppm by weight.
The term "optional" as used herein means either with or without, and with or without the addition of.
The term "≦" for a component defined as a range means that a component may be optionally or selectively added. For example, "200 ppm by weight or less of the metal element in the co-adjuvant of the rhenium adjuvant" means that the metal element in the co-adjuvant of the rhenium adjuvant is an optional added component and is contained in an amount of 0ppm by weight or less of the metal element in the co-adjuvant of the rhenium adjuvant 200ppm by weight or less.
The term "co-promoter for rhenium promoter" as used herein is also referred to as "co-promoter for rhenium".
The method for preparing the silver catalyst according to the third aspect of the present invention according to the fourth aspect of the present invention may be a method for preparing a silver catalyst according to the third aspect of the present invention, which comprises immersing the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared according to the second aspect of the present invention in a solution containing a silver compound, an organic amine compound and an auxiliary agent, followed by activation heat treatment; the aid comprises an alkali metal aid, an alkaline earth metal aid, a rhenium aid and an optional rhenium aid co-aid.
In the above silver catalyst preparation method, the organic amine compound may be any organic amine compound suitable for preparing a silver catalyst for ethylene oxide production, as long as the organic amine compound is capable of forming a silver amine complex with a silver compound, such as pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine, or a mixture thereof; preferably, the organic amine compound is a mixture of ethylenediamine and ethanolamine.
In the above method for preparing a silver catalyst, the alkali metal promoter may be a compound of lithium, sodium, potassium, rubidium or cesium or a compound of any one thereof, such as a nitrate, sulfate or hydroxide thereof, or a combination of any two or more of the foregoing compounds; preferably, the alkali metal assistant is cesium sulfate and/or cesium nitrate.
In the above method for preparing a silver catalyst, the alkaline earth metal promoter may be a compound of magnesium, calcium, strontium or barium, such as an oxide, oxalate, sulfate, acetate or nitrate thereof, or a combination of any two or more of the foregoing compounds; preferably, the alkaline earth metal auxiliary agent is a compound of barium and/or strontium; more preferably, the alkaline earth metal auxiliary agent is barium acetate and/or strontium acetate. The alkaline earth metal promoter may be applied to the support before, simultaneously with, or after impregnation of the silver, or may be impregnated on the support after the silver compound has been reduced.
In the preparation method of the silver catalyst, the rhenium assistant can be rhenium oxide, perrhenic acid, perrhenate or a mixture thereof; preferred rhenium promoters are perrhenic acid and perrhenates such as perrhenic acid, cesium perrhenate, ammonium perrhenate and the like. The co-promoter of the rhenium promoter may be a compound of any transition metal in the periodic table of elements, or a mixture of several transition metal compounds, the metal in the co-promoter of the rhenium promoter is preferably selected from the group consisting of elements in group VIB and group VIIB, and the co-promoter of the rhenium promoter may include oxyacids of elements in group VIB and group VIIB and salts thereof, such as at least one of tungstic acid, cesium tungstate, molybdic acid, ammonium molybdate and cerium sulfate. The rhenium promoter and the co-promoter of the rhenium promoter may be applied to the carrier before, simultaneously with, or after impregnation of the silver, or may be impregnated on the carrier after the silver compound has been reduced. The activity, selectivity, and stability of activity and selectivity of the resulting silver catalyst can be further improved by the addition of a rhenium promoter and a co-promoter for the rhenium promoter.
According to some embodiments of the present invention, the method for preparing the silver catalyst comprises the steps of:
(1) impregnating the porous alpha-alumina support with a solution containing a sufficient amount of a co-promoter of a silver compound, an organic amine compound, an alkali metal promoter, an alkaline earth metal promoter, a rhenium promoter and a rhenium promoter;
(2) filtering to remove the impregnation solution, and drying the impregnated carrier;
(3) activating the impregnated carrier obtained in the step (2) in oxygen-containing mixed gas to prepare the silver catalyst.
In some specific embodiments of the present invention, firstly, the silver oxalate is dissolved by using the aqueous solution of ethylenediamine and ethanolamine to prepare a silver amine solution, and then the above-mentioned auxiliary agents are added to prepare a steeping liquor; then soaking the alpha-alumina carrier by using the prepared impregnation liquid, draining, and carrying out thermal decomposition in air flow or nitrogen-oxygen mixed gas with oxygen content not more than 21 percent (such as oxygen content of 8.0 percent) at the temperature range of 180-700 ℃, preferably 200-500 ℃ for 0.5-120 minutes, preferably 1-60 minutes to prepare the finished product of the silver catalyst.
The method for producing ethylene oxide by the epoxidation of ethylene according to the fifth aspect of the present invention comprises subjecting ethylene to the epoxidation reaction in the presence of the silver catalyst described above or the silver catalyst prepared by the above method in a reaction apparatus, which may be any apparatus capable of performing the epoxidation reaction.
The method for detecting the physical property of the alpha-alumina carrier and the performance of the silver catalyst comprises the following steps:
the specific surface area of the support is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.
The porosity, pore volume and pore structure distribution of the carrier are measured by mercury intrusion method. For example, the pore volume of the support can be determined using an AutoPore9510 model mercury porosimeter, a company mike, usa.
The lateral pressure strength of the carrier can be obtained by, for example, randomly selecting 30 carrier samples by using a DL II type intelligent particle strength tester produced by the institute of chemical engineering and design, measuring the radial crushing strength, and averaging.
Determination of catalyst Performance: various silver catalysts involved in the present invention were tested for their initial activity and selectivity using a laboratory microreactor (hereinafter referred to as "microreaction") evaluation device. The reactor used in the microreaction evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reactor was placed in a heating mantle. The filling volume of the catalyst is 1mL, and the lower part of the catalyst is provided with an inert filler, so that a catalyst bed layer is positioned in a constant temperature area of a heating sleeve.
The measurement conditions for the activity and selectivity of the catalyst used in the present invention are shown in Table 1:
TABLE 1 determination of catalyst Activity and selectivity
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The measurement results were corrected for volume shrinkage and the selectivity S was calculated as follows:
wherein, Delta EO is the difference of the concentration of ethylene oxide in the outlet gas and the inlet gas of the reactor, Delta CO 2 The carbon dioxide concentration difference between the outlet gas and the inlet gas of the reactor is determined, and the average of more than 10 groups of test data is taken as the test result of the day.
According to the invention, micron-sized alpha-alumina crystal grains and a silicon-containing auxiliary agent are added in a certain proportion in the preparation process of the carrier, and the carrier prepared by high-temperature roasting has ideal porosity, specific surface area and pore structure, wherein 0.5-1.5 mu m pores account for 40-60% (by volume) in pore distribution, and 5-0 mu m pores account for 10-30% (by volume). Compared with the prior art, the silver catalyst prepared by the carrier provided by the invention has the advantages of high activity and good selectivity for the reaction of producing ethylene oxide by ethylene epoxidation.
Examples
Example 1:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 4750g of pseudo-monohydrate A1 smaller than 75 μm 2 O 3 1190g, 3-8 μm of alpha-A1 2 O 3 60g of barium nitrate, 21g of barium nitrate and 18g of silicon dioxide are put into a mixer and mixed uniformly, then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and oven drying at 80-120 deg.C for more than 2 hr to reduce free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining at 1350 ℃ for 8 hours to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) Preparation of the catalyst: 980g of ethylenediamine and 255g of ethanolamine are dissolved in 1500g of deionized water, silver oxalate is slowly added into the mixed solution under stirring, the temperature is kept below 40 ℃, so that the silver oxalate is completely dissolved, the addition amount of the silver oxalate is 13 percent (weight) of silver content in the silver catalyst calculated by silver element, 9.0g of cesium nitrate, 7.8g of strontium acetate, 4.4g of perrhenic acid, 1.0g of cerium sulfate and deionized water are added to make the total mass of the solution reach 5000g, and impregnation liquid is prepared for later use.
Collecting 2500g of carrier sample, placing into vacuum-pumping container, vacuum-pumping to above 10mmHg, introducing the above immersion liquid, maintaining for 30min, and leaching to remove excessive solution. And heating the impregnated carrier in air flow at 450 ℃ for 3min, and cooling to obtain the silver catalyst.
The activity and selectivity of the catalyst samples were measured using a microreactor evaluation unit under the aforementioned process conditions, and the results of the microreaction evaluation are shown in Table 3.
Example 2:
(1) preparation of the carrier: mixing 25-300 μm trihydrate alpha-A1 2 O 3 4700g，Pseudo-monohydrate A1 of less than 75 μm 2 O 3 1180g, 3-8 μm of alpha-A1 2 O 3 120g of barium nitrate, 21g of barium nitrate and 18g of silicon dioxide are put into a mixer to be uniformly mixed, and then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3, weight ratio) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and oven drying at 80-120 deg.C for more than 2 hr to reduce free water content to below 10%. The kneaded and molded carrier is put into a bell jar kiln, is heated from room temperature to 1350 ℃ for 33 hours and is calcined for 10 hours at 1350 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 3:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 4320g, pseudo-monohydrate A1 less than 75 μm 2 O 3 1080g, 3-8 μm alpha-A1 2 O 3 600g, 21g of barium nitrate and 18g of silicon dioxide are put into a mixer to be uniformly mixed, and then are transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3, weight ratio) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and oven drying at 80-120 deg.C for more than 2 hr to reduce free water content to below 10%. The carrier after the kneading and molding is put into a bell jar kiln, is heated from room temperature to 1380 ℃ for 33 hours, and is calcined for 7 hours at 1380 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 4:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 3850g, less than 75 μm pseudo-monohydrate A1 2 O 3 950g, 3-8 μm of alpha-A1 2 O 3 1200g of barium nitrate, 21g of barium nitrate and dioxide18g of silicon is put into a mixer to be mixed uniformly, and then transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. The kneaded and molded carrier is put into a bell jar kiln, heated from room temperature to 1420 ℃ over 33 hours, and calcined at 1420 ℃ for 10 hours to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 5:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 3600g, pseudo-monohydrate A1 less than 75 μm 2 O 3 900g, 3-8 μm of alpha-A1 2 O 3 1500g of barium nitrate, 21g of barium nitrate and 18g of silicon dioxide are placed in a blender and mixed evenly, then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and oven drying at 80-120 deg.C for more than 2 hr to reduce free water content to below 10%. The carrier after the kneading and forming is put into a bell jar kiln and is heated from room temperature to 1450 ℃ for 33 hours, and the carrier is calcined for 10 hours at 1450 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 6:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 3600g of pseudo-monohydrate A1 smaller than 75 μm 2 O 3 900g, 3-8 μm of alpha-A1 2 O 3 1500g of barium nitrate, 21g of barium nitrate and 18g of silicon dioxide are put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water is 1:3 by weight) are added,kneading into paste capable of being extruded and molded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. The kneaded and molded carrier is put into a bell jar kiln, the room temperature is raised to 1480 ℃ after 33 hours, and the carrier is calcined for 10 hours at the temperature of 1480 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 1:
(1) preparation of the carrier: mixing 25-300 μm trihydrate alpha-A1 2 O 3 4800g of pseudo-monohydrate A1 smaller than 75 μm 2 O 3 1200g，NH 4 150g of F and 21g of barium nitrate are put into a blender and mixed evenly, then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. The kneaded and molded carrier is put into a bell jar kiln, is heated from room temperature to 1250 ℃ for 33 hours and is calcined for 5 hours at 1250 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 2:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 4800g of pseudo-monohydrate A1 smaller than 75 μm 2 O 3 1200g，NH 4 150g of F, 21g of barium nitrate and 18g of silicon dioxide are put into a blender and mixed evenly, then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water is 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and oven drying at 80-120 deg.C for more than 2 hr to reduce free water content to below 10%. Will be at the topThe kneaded and molded carrier is put into a bell jar kiln, is heated from room temperature to 1250 ℃ for 33 hours and is calcined for 8 hours at 1250 ℃ to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 3:
(1) preparation of the carrier: mixing 25-300 μm of trihydrate alpha-A1 2 O 3 4800g of pseudo-monohydrate A1 smaller than 75 μm 2 O 3 1200g of barium nitrate, 21g of barium nitrate and 18g of silicon dioxide are placed in a blender and mixed uniformly, then the mixture is transferred into a kneader, 42g of vaseline and 2100mL of dilute nitric acid (nitric acid: water: 1:3 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining at 1350 ℃ for 4 hours to obtain white alpha-A1 2 O 3 And (3) a carrier. The measured physical properties of the carrier and the pore structure distribution data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
TABLE 2 physical Properties and pore Structure distribution data of the vectors
TABLE 3 Properties of the catalysts
As can be seen by comparing the data in tables 2 and 3, the carrier prepared by adding a certain proportion of micron-sized alpha-alumina crystal grains and a silicon-containing auxiliary agent in the preparation process of the carrier has ideal porosity, specific surface area and pore structure, and the silver catalyst prepared by the carrier has high activity and selectivity in the reaction of producing ethylene oxide by ethylene epoxidation.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified as prescribed without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (12)
1. An alpha-alumina carrier of a silver catalyst for ethylene epoxidation is prepared by molding, drying and roasting an alpha-alumina carrier precursor mixture, wherein the alpha-alumina carrier precursor mixture consists of the following components:
based on the total weight of the solid components a-e,
the carrier comprises 40-60% (volume) of pores with pore diameter of 0.5-1.5 μm and 10-30% (volume) of pores with pore diameter of 5-10 μm, based on the total pore volume.
2. The α -alumina support according to claim 1, wherein the α -alumina support precursor mixture consists of, based on the total weight of solid components a-e:
3. the alpha-alumina carrier according to claim 1 or 2,
the heavy alkaline earth metal compound comprises one or more of oxides, sulfates, acetates, nitrates and oxalates of heavy alkaline earth metals;
the silicon-containing auxiliary agent comprises silicate and/or silicon oxide;
the burnout lubricating material is selected from one or more of petroleum coke, carbon powder, graphite and vaseline;
the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
4. An alpha-alumina support according to claim 3, wherein the heavy alkaline earth metal is strontium and/or barium.
5. The α -alumina carrier as claimed in claim 1 or 2, wherein the crush strength of the carrier is 40 to 160N/pellet; the specific surface area is 0.7-2.5m 2 (ii)/g; the pore volume is 0.35-0.75 ml/g.
6. The α -alumina carrier as claimed in claim 5, wherein the crush strength of the carrier is 60 to 130N/pellet; the specific surface area is 0.9-1.8m 2 (ii)/g; the pore volume is 0.45-0.70 ml/g.
7. A method of preparing an α -alumina support as claimed in any one of claims 1 to 6, which comprises:
step S1, mixing the components a-e to form a solid mixture;
step S2, mixing the component f and the component g with the solid mixture to prepare an alpha-alumina carrier precursor mixture;
and step S3, forming the alpha-alumina carrier precursor mixture, drying and roasting to obtain the alpha-alumina carrier.
8. The method as claimed in claim 7, wherein in step S3, the baking temperature is 1350-1480 ℃.
9. A silver catalyst for the epoxidation of ethylene comprising the following components, based on the total weight of the catalyst:
component i, an α -alumina support as defined in any one of claims 1 to 6 or an α -alumina support prepared by a process as defined in claim 7 or 8;
10. the silver catalyst according to claim 9, characterized in that it comprises the following components, based on the total weight of the catalyst:
component i, an α -alumina support as defined in any one of claims 1 to 6 or an α -alumina support prepared by a process as defined in claim 7 or 8;
11. a method for preparing the silver catalyst according to claim 9 or 10, which comprises immersing the α -alumina carrier according to any one of claims 1 to 6 or the α -alumina carrier prepared by the method according to claim 7 or 8 in a solution containing a silver compound, an organic amine compound and an auxiliary agent, followed by activation heat treatment; the aid comprises an alkali metal aid, an alkaline earth metal aid, a rhenium aid and an optional co-aid of the rhenium aid.
12. A process for the production of ethylene oxide by epoxidation of ethylene in the presence of a silver catalyst according to claim 9 or 10 or a silver catalyst prepared by the process according to claim 11.
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| CN109499558B (en) * | 2017-09-15 | 2021-09-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst and olefin epoxidation method |
| CN109499560B (en) * | 2017-09-15 | 2021-04-09 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN107902745B (en) * | 2017-11-30 | 2021-08-17 | 浙江奇彩环境科技股份有限公司 | Treatment method of landfill leachate concentrated water |
| CN110038543B (en) * | 2018-01-17 | 2022-07-12 | 中国石油化工股份有限公司 | Alpha-alumina carrier of silver catalyst for ethylene epoxidation, silver catalyst and method for producing ethylene oxide by ethylene epoxidation |
| CN110354910B (en) * | 2018-03-26 | 2021-12-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method and application thereof |
| CN111437888A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | α -alumina carrier, silver catalyst for ethylene epoxidation and application |
| CN114100595A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene epoxidation and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation |
| CN116726919B (en) * | 2023-05-22 | 2024-04-09 | 大连瑞克科技股份有限公司 | Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof |
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