CN109499558B - Alpha-alumina carrier, silver catalyst and olefin epoxidation method - Google Patents
Alpha-alumina carrier, silver catalyst and olefin epoxidation method Download PDFInfo
- Publication number
- CN109499558B CN109499558B CN201710832849.9A CN201710832849A CN109499558B CN 109499558 B CN109499558 B CN 109499558B CN 201710832849 A CN201710832849 A CN 201710832849A CN 109499558 B CN109499558 B CN 109499558B
- Authority
- CN
- China
- Prior art keywords
- alumina
- alpha
- carrier
- silver catalyst
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 140
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 83
- 239000004332 silver Substances 0.000 title claims abstract description 83
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 19
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001679 gibbsite Inorganic materials 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- -1 propylene, ethylene Chemical group 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 6
- 229910001680 bayerite Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000004684 trihydrates Chemical class 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 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 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910001682 nordstrandite Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 14
- 239000000654 additive Substances 0.000 description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229940100890 silver compound Drugs 0.000 description 6
- 150000003379 silver compounds Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 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 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- B01J35/51—
-
- B01J35/612—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention relates to the field of catalysts, and discloses an alpha-alumina carrier, a silver catalyst and an olefin epoxidation method, wherein the alpha-alumina carrier is prepared by the following steps: step S1, preparing a solid powder having the following composition: mixing the solid powder with a binder and water to obtain a mixture; step S2, molding the mixture obtained in the step S1 to obtain a molded body; step S3, drying and roasting the formed body obtained in the step S2. The alpha-alumina carrier has a proper surface area and pore structure, the particles present a small and thick spheroidal appearance, and are different from alpha-alumina carriers with lamellar appearances, so that the silver catalyst prepared by the carrier shows good selectivity and stability in olefin epoxidation reaction, and the activity is not reduced.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to an alpha-alumina carrier, a silver catalyst prepared from the alpha-alumina carrier and application of the silver catalyst. More particularly, the present invention relates to an α -alumina carrier for a silver catalyst for olefin epoxidation to produce epoxy compounds, a silver catalyst prepared from the carrier, and a method for olefin epoxidation using the catalyst.
Background
Ethylene oxide is an important organic chemical raw material, is second to polyethylene and polyvinyl chloride in the ethylene derivative, is mainly used for producing ethylene glycol, is a very important fine chemical raw material, can derive various fine chemical products such as nonionic surfactant, ethanolamine, glycol ether and the like, and further produces four to five thousand products such as detergent, emulsifier, antifreeze, plasticizer, lubricant, pesticide and the like.
To date, silver catalysts remain the only catalyst commercially effective for the epoxidation of ethylene to ethylene oxide. In the prior art, silver catalysts usually have, in addition to the silver component, one or more other elements co-deposited therewith for improving the catalytic performance of the silver catalyst on a carrier, which usually consists of alpha-alumina having a suitable specific surface and pore structure, which is resistant to high temperatures. Under the action of silver catalyst, ethylene is oxidized to produce ethylene oxide and side reaction to produce carbon dioxide and water, and the activity, selectivity and stability are the main performance indexes of silver catalyst. By activity is meant the reaction temperature required for the ethylene oxide production process to reach a certain reaction load. 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, with a smaller rate of decrease giving better catalyst stability. 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 'three-high' silver catalyst with high activity, high selectivity and good stability is the main direction of the research of the silver catalyst. However, in general, the activity and selectivity of silver catalysts are mutually limiting. 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.
CN102133544A discloses a preparation method of an alpha-alumina carrier, which comprises mixing industrial alpha-alumina trihydrate, pseudo-alumina monohydrate, 0-30% of burnout pore-forming material, 0-2.5% of alkaline earth metal salt, 0-3% of fluoride, a binder and water, wherein the percentages are based on the total mass of raw material alumina, the weight ratio of the alpha-alumina trihydrate to the pseudo-alumina monohydrate is 1-4:1, and the total amount of the binder and the water is 15-30% of the total weight of the raw material alumina; then the alpha-alumina carrier is obtained by extrusion forming, drying and roasting. In this method, the pore expansion is performed using 0-30% of carbon monoxide and/or carbon dioxide gas released from the burnout carbonaceous material.
US4410453 discloses an alpha-alumina carrier containing zinc, lanthanum, magnesium elements, which are added as alumina or oxide precursor during the preparation of the carrier, which is used in a silver catalyst for ethylene oxidation to ethylene oxide, the silver catalyst prepared by introducing zinc oxide, lanthanum oxide or magnesium oxide into the carrier having better activity and selectivity. US5100859, US5145824, EP0900126, US5801259, US5733842 and the like add alkaline earth metals, preferably calcium, strontium and barium salts, and zirconium compounds to alpha-alumina to prepare a carrier, and the carrier is used together with the zirconium compounds to prepare the silver catalyst with better selectivity.
Although the above patent documents are improved in terms of improving the α -alumina carrier and adding the carrier assistant, respectively, and the catalytic performance of the prepared silver catalyst is improved, there is still a need in the art for an alumina carrier and a corresponding silver catalyst with better catalytic olefin epoxidation performance, especially a silver catalyst with good selectivity and stability under the condition of environmental protection of the preparation process and without reducing the activity of the silver catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an alpha-alumina carrier, a silver catalyst taking the alpha-alumina carrier as a carrier and an olefin epoxidation method using the catalyst. After the alpha-alumina carrier is loaded with silver and preferably various active components to prepare the silver catalyst, the silver catalyst shows good selectivity and stability in olefin epoxidation reaction, and the activity is not reduced.
In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and intensive studies in the field of improving the performance of silver catalysts, and found that an α -alumina carrier having a suitable surface area and pore structure, which is different from an α -alumina carrier having a lamellar morphology, is prepared using composite-phase alumina instead of a pore-forming agent (e.g., burnable lubricant) and various expensive auxiliary agents during the preparation of the carrier, and that the α -alumina particles of the present invention exhibit a small and thick spheroidal appearance morphology, so that the silver catalyst prepared from the carrier exhibits excellent selectivity and stability in olefin epoxidation without a decrease in activity.
In order to achieve the above object, according to one aspect of the present invention, there is provided an α -alumina support prepared by a method comprising:
step S1, preparing a solid powder having the following composition: mixing the solid powder with a binder and water to obtain a mixture;
step S2, molding the mixture obtained in the step S1 to obtain a molded body;
step S3, drying and roasting the formed body obtained in the step S2 to obtain the alpha-alumina carrier;
the alpha-alumina carrier has a spheroidal appearance.
The second aspect of the invention provides a silver catalyst for olefin epoxidation, which comprises a carrier and an active component silver loaded on the carrier, wherein the carrier is the alpha-alumina carrier provided by the invention.
In a third aspect of the present invention, there is provided a process for the epoxidation of an olefin, wherein the process comprises subjecting an olefin to an olefin epoxidation reaction in the presence of the silver catalyst for olefin epoxidation according to the present invention to obtain an epoxy compound.
The alpha-alumina carrier has a proper surface area and pore structure, the particles present a small and thick spheroidal appearance, and are different from alpha-alumina carriers with lamellar appearances, so that the silver catalyst prepared by the carrier shows good selectivity and stability in olefin epoxidation reaction, and the activity is not reduced. In addition, the preparation process is environment-friendly and the material cost is low.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
Fig. 1 is an electron micrograph of an α -alumina support according to a preferred embodiment of the present invention.
Detailed Description
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to the invention, the alpha-alumina carrier is prepared by a method comprising the following steps:
step S1, preparing a solid powder having the following composition: mixing the solid powder with a binder and water to obtain a mixture;
step S2, molding the mixture obtained in the step S1 to obtain a molded body;
step S3, drying and roasting the formed body obtained in the step S2 to obtain the alpha-alumina carrier;
the alpha-alumina carrier has a spheroidal appearance.
In the present invention, "optionally contained" means that the mixture may or may not contain the compound.
According to the invention, the composite phase alumina comprises at least two of gamma-alumina, theta-alumina, kappa-alumina, eta-alumina and alpha-alumina. Preferably, the composite phase alumina is a composite phase alumina calcined by aluminum hydroxide, more preferably, the composite phase alumina is calcined by aluminum hydroxide at 750-1100 ℃, and the aluminum hydroxide is preferably gibbsite and/or bayerite.
Although the α -alumina particles having a suitable surface area and pore structure exhibiting a small and thick spheroidal appearance can be prepared by using the composite-phase alumina in the preparation of the α -alumina support according to the present invention, it is preferable that the composite-phase alumina is contained in an amount of 1 to 70% by weight, preferably 5 to 40% by weight, and more preferably 8 to 30% by weight, based on the total weight of the solid components in the mixture, in accordance with a preferred embodiment of the present invention, from the viewpoint of further improving the performance of the α -alumina support.
According to the present invention, in order to further improve the performance of the alpha-alumina carrier, an alkaline earth metal compound is also added during the preparation of the alpha-alumina carrier. The alkaline earth metal compound is preferably selected from one or more of oxides, sulfates, nitrates, acetates and oxalates of strontium and/or barium. The content of the alkaline earth metal compound is preferably 0.1 to 5% by weight, based on the total weight of the solid powder.
In the present invention, the alumina trihydrate is an optionally contained component, preferably selected from one or more of nordstrandite, gibbsite and bayerite. According to a preferred embodiment of the invention, the weight ratio of alumina trihydrate to pseudoboehmite is from 0 to 4: 1. the catalyst prepared by the carrier containing the alumina trihydrate in the range has better selectivity and stability.
According to the invention, in order to accelerate the crystal transformation of the alumina, a fluorine-containing compound is also added in the process of preparing the alpha-alumina carrier. The fluorine-containing compound of the present invention is preferably selected from one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride. The fluorine-containing compound is preferably contained in an amount of 0 to 3% by weight based on the total weight of the solid powder.
During the preparation of the alpha-alumina carrier, a binder is usually added, which forms an alumina sol with the pseudoboehmite in the solid powder, binding the components together and forming an extrudable paste. The binder comprises one or more of citric acid, nitric acid, hydrochloric acid, formic acid and acetic acid, more preferably nitric acid, and the binder and the pseudo-boehmite can be replaced by aluminum sol in whole or in part. Preferably, the weight ratio of the binder to water is 1: 1-10; the weight ratio of the total weight of the binder and the water to the solid powder is 1: 2-10.
According to the present invention, in step S1, the mixture is prepared by a method known to those skilled in the art, for example, by uniformly mixing the composite phase alumina, alumina trihydrate, alkaline earth metal compound, and fluorine-containing compound to obtain a solid powder, and adding the binder and water to obtain a mixture.
The process for obtaining the shaped body in step S2 according to the present invention may be carried out according to conventional techniques in the art. Wherein, the shape of the formed body can be annular, spherical, cylindrical or porous cylindrical. Wherein, the solid powder is added with a binder and water to obtain a mixture which needs to be kneaded in a kneader, the kneading time can be 20-60min, the mixture is kneaded into paste which can be extruded and formed, and the paste is formed in a forming machine to form a single-hole or multi-hole column.
According to the present invention, the drying and firing method in the step S3 may be performed in a conventional manner in the art. Preferably, the molded article may be dried to contain free water in an amount of 10 wt% or less, the drying temperature may be 20 to 100 ℃, and the drying time may be controlled to 20 to 48 hours depending on the moisture content. The roasting time can be 2-48 hours, and the roasting temperature can be 1200-1500 ℃.
The alumina carrier of the invention has the following characteristics: the alpha-alumina component accounts for more than or equal to 98 percent of the total weight of the carrier, and the specific surface area is 0.5-3.5m2The pore volume is 0.3-1.0mL/g, the most probable pore diameter is 0.1-30.0 μm, the water absorption is not less than 40%, and the crushing strength is 30-400N/particle, preferably 40-300N/particle, more preferably 120-250N/particle, and most preferably 150-230N/particle.
In the invention, the lateral crushing strength of the alumina carrier is obtained by selecting a carrier sample and measuring the radial crushing strength and then taking an average value by adopting a DL II type intelligent particle strength measuring instrument; the water absorption is measured by a density method; the specific surface area is measured by adopting a nitrogen physical adsorption BET method; the pore distribution was determined by mercury intrusion.
According to another aspect of the invention, the invention also provides a silver catalyst for olefin epoxidation, which comprises a carrier and an active component silver loaded on the carrier, wherein the carrier is the alpha-alumina carrier provided by the invention.
According to a preferred embodiment of the present invention, the silver catalyst further comprises:
alkali and/or alkaline earth metals or compounds based on alkali and/or alkaline earth metals;
rhenium metal and/or rhenium-based compounds; and
optionally, a rhenium co-promoter element selected from one or more of cerium, sulfur, molybdenum, chromium, oxyanions in salt or acid form.
After preparing the alpha-alumina carrier of the present invention, the silver catalyst of the present invention may be prepared by a known manner or any conventional manner by those skilled in the art. Such as by impregnating the above-described alpha-alumina carrier with a solution containing sufficient amounts of an organic amine, a silver compound, an alkali metal promoter, an alkaline earth metal promoter, optionally a rhenium promoter and a co-promoter for the rhenium promoter.
According to a preferred embodiment of the present invention, the silver catalyst is prepared by a method comprising the steps of: i) impregnating an alpha-alumina carrier prepared according to the method of the invention with a solution containing sufficient amounts of an organic amine, a silver compound, an alkali metal promoter, an alkaline earth metal promoter, optionally a rhenium promoter and a co-promoter for the rhenium promoter; II) leaching the impregnation liquid; III) activating the carrier obtained in the step II) in oxygen-containing gas to prepare the silver catalyst.
In the present invention, the organic amine is added to be able to form a silver amine complex with the silver compound during the preparation of the silver catalyst. The organic amine may be selected from one or more of 1, 2-propanediamine, 1, 3-propanediamine, ethylenediamine, 1, 2-butanediamine, 1, 3-butanediamine, pyridine, ethylamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, ethanolamine, propanolamine and butanolamine.
In the preparation process of the silver catalyst, the silver compound can be selected from one or more of silver oxide, silver nitrate and silver oxalate, and the mass of the silver element accounts for 10-40% of the mass of the silver catalyst.
In the invention, the alkali metal promoter can be one or more selected from lithium, sodium, potassium, rubidium and cesium, and the mass of the alkali metal promoter accounts for 5-2000ppm of the mass of the silver catalyst.
In the invention, the alkaline earth metal promoter can be selected from one or more of magnesium, calcium, strontium and barium, and the mass of the alkaline earth metal promoter accounts for 5-20000ppm of the mass of the silver catalyst.
In the invention, the rhenium promoter can be one or more selected from rhenium oxide, ammonium perrhenate, perrhenic acid and cesium perrhenate, and the mass of the rhenium promoter accounts for 50-10000ppm of the mass of the silver catalyst.
In the present invention, the co-promoter of the rhenium promoter may be selected from one or more of cerium, sulfur, molybdenum, chromium, oxyanions in salt or acid form.
In the preparation process of the silver catalyst, in order to fully impregnate the alpha-alumina carrier prepared by the method of the invention with a solution containing sufficient amounts of organic amine, silver compound, alkali metal additive, alkaline earth metal additive, optional rhenium additive and rhenium additive co-additive, the alpha-alumina carrier is usually impregnated under the condition of vacuum degree less than 10mmHg for 5-60 min. Leaching the impregnation solution after impregnation, and activating in air or nitrogen-oxygen mixed gas with oxygen content not more than 21% by volume at the activation temperature of 150-400 ℃ for 1-120 min.
In the invention, in order to prepare the silver catalyst, firstly, the aqueous solution of silver nitrate reacts with the aqueous solution of ammonium oxalate or oxalic acid to separate out silver oxalate precipitate, the silver oxalate precipitate is filtered and washed by deionized water until no nitrate ions exist, then the silver oxalate is dissolved in the aqueous solution of organic amine, an alkali metal additive, an alkaline earth metal additive, an optional rhenium additive and a co-additive of a rhenium additive are added to prepare an impregnating solution, the alpha-alumina carrier prepared by the method is impregnated by the impregnating solution, and the impregnating solution is leached and activated to finally prepare the silver catalyst.
In order to obtain silver catalysts with higher silver content and/or promoter content, the present invention may prepare silver-containing catalysts by one or more impregnation processes.
The assistants such as alkali metal, alkaline earth metal, rhenium assistant and rhenium co-assistant added in the preparation process of the silver catalyst can be deposited on the carrier before, simultaneously with or after silver impregnation, and can also be deposited on the carrier after the silver compound is activated and reduced.
According to another aspect of the present invention, the present invention also provides a method for the epoxidation of an olefin, wherein the method comprises subjecting the olefin to the epoxidation reaction under the action of the silver catalyst to obtain an epoxy compound. Wherein the olefin may include one or more of styrene, propylene, ethylene, and 1, 3-butadiene. The olefin epoxidation reaction apparatus may be any apparatus capable of carrying out an epoxidation reaction.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
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 catalytic performance of silver catalyst:
the activity and selectivity of various silver catalysts of the invention were tested using a laboratory microreactor evaluation apparatus. The reactor used in the microreactor evaluation apparatus was a stainless steel reaction tube having an inner diameter of 4mm, which 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 shown in Table 1.
TABLE 1
When the above reaction conditions were stably achieved, the reactor inlet and outlet gas compositions were continuously measured. The selectivity was calculated after volume shrinkage correction of the measurement results according to the following formula:
selectivity is
Where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2The 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.
In the following examples, the lateral crushing strength of the alumina carrier is obtained by selecting an alumina carrier sample by a DL II type intelligent particle strength tester, measuring the radial crushing strength and then averaging; the water absorption is measured by a density method; the specific surface area is measured by adopting a nitrogen physical adsorption BET method; the pore distribution was determined by mercury intrusion.
Example 1
(1) Preparation of the carrier:
roasting gibbsite at 950 ℃ for 10h to obtain gamma-alumina and kappa-alumina composite phase alumina, weighing 100g of composite phase alumina, 360.0g of gibbsite, 240.0g of pseudo-boehmite, 8.0g of ammonium fluoride and 5.0g of barium sulfate, putting the materials into a mixer, uniformly mixing, transferring the materials into a kneader, adding dilute nitric acid (nitric acid: water: 1: 3, volume ratio) until the materials are kneaded into paste capable of being extruded, putting the paste into a bar extruder, extruding the paste into a seven-hole column, drying the seven-hole column at 60-120 ℃ for more than 24h to reduce the free water content to below 10 wt%, roasting the dried seven-hole column at 1350 ℃, roasting at constant temperature for 10h, and finally cooling to room temperature to obtain the alpha-alumina carrier. The alpha-alumina carrier prepared in the embodiment 1 is named as Scar-1 in number, relevant physical property data are shown in a table 2, an electron micrograph is shown in a figure 1, and as can be seen from the figure 1, the alpha-alumina particles of the invention have small and thick sphere-like appearance morphology which is different from the lamella morphology of the alpha-alumina carrier in the prior art.
(2) Preparation of the catalyst:
weighing 140g of silver nitrate and dissolving the silver nitrate in 150ml of deionized water, weighing 64g of ammonium oxalate and dissolving the ammonium oxalate in 520ml of deionized water to obtain a silver nitrate solution and an ammonium oxalate solution, mixing the two solutions under vigorous stirring to generate a white silver oxalate precipitate, aging for more than 30 minutes, filtering, and washing the precipitate with deionized water until no nitrate ions exist. The filter cake contained about 60% silver and about 15% water. Adding 60g of ethylenediamine, 22g of ethanolamine and 75g of deionized water into a glass flask with stirring to prepare a mixed solution, slowly adding the prepared silver oxalate paste into the mixed solution, continuously stirring to completely dissolve the silver oxalate, wherein the adding amount of the silver oxalate ensures that the prepared impregnation solution contains 22 mass percent of silver, then sequentially adding 0.35g of cesium acetate, 0.50g of barium acetate and 0.70g of ammonium perrhenate, adding deionized water to ensure that the total mass of the solution reaches 400g, and uniformly mixing to prepare the impregnation solution for later use. 20g of Scar-1 carrier was placed in a vacuum vessel, the prepared impregnating solution was poured into the vessel, the carrier was immersed, vacuum was applied to less than 10mmHg for about 30min, and excess solution was leached away. And finally, placing the impregnated carrier in air at 300 ℃ for heating for 3min, and cooling to obtain the silver catalyst.
(3) Evaluation of catalyst Performance:
the resulting catalyst samples were tested for activity and selectivity at various times using a microreactor evaluation apparatus under the process conditions described above, and the results are shown in Table 3.
Example 2
(1) Preparation of the carrier:
gibbsite was calcined at 1080 ℃ for 10 hours to obtain theta-alumina and kappa-alumina composite phase alumina, and 60g of this composite phase alumina was weighed in place of the composite phase alumina in example 1, except that the procedure was as in example 1. The alpha-alumina carrier prepared in example 2 was designated as Scar-2, and the relevant physical property data are shown in Table 2.
(2) Preparation of the catalyst:
the preparation method of the silver catalyst in example 1 was the same, except that the alpha-alumina support was modified correspondingly to the scarr-2 numbered alpha-alumina support prepared in example 2.
(3) Evaluation of catalytic performance of silver catalyst:
the activity and selectivity of the catalyst at various stages were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
Example 3
(1) Preparation of the carrier:
roasting bayerite at 900 ℃ for 10h to obtain composite phase alumina of theta-alumina and alpha-alumina, weighing 200g of composite phase alumina, 360.0g of gibbsite, 240.0g of pseudo-boehmite, 8.0g of ammonium fluoride and 5.0g of barium sulfate, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding dilute nitric acid (nitric acid: water: 1: 3, volume ratio) until kneading into paste capable of being extruded, putting the paste into a strip extruder, extruding into a seven-hole column, drying at 60-120 ℃ for more than 24h to reduce the free water content to below 10%, roasting the dried seven-hole column at 1200 ℃, roasting at constant temperature for 10h, and finally cooling to room temperature to obtain the alpha-alumina carrier. The alpha-alumina carrier prepared in example 3 was designated as Scar-3, and the data on the relevant physical properties are shown in Table 2.
(2) Preparation of the catalyst:
the preparation method of the silver catalyst in example 1 was the same, except that the alpha-alumina support was modified correspondingly to the scara-3 numbered alpha-alumina support prepared in example 3.
(3) Evaluation of catalytic performance of silver catalyst:
the activity and selectivity of the catalyst at various stages were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
Example 4
(1) Preparation of the carrier:
calcining gibbsite at 1050 ℃ for 10h, calcining bayerite at 850 ℃ for 10h, mixing and calcining the products according to the mass ratio of 1:1 to obtain composite phase alumina of kappa-alumina and theta-alumina, weighing 300g of composite phase alumina, 360.0g of gibbsite, 240.0g of pseudo-boehmite, 8.0g of ammonium fluoride and 5.0g of barium sulfate, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding dilute nitric acid (1: 3 (volume ratio) nitric acid: water) until kneading into paste capable of being extruded, putting the paste into a bar extruder, extruding into seven-hole column, drying at 60-120 deg.C for more than 24 hr to reduce free water content to below 10%, and then roasting the dried seven-hole column at 1400 ℃ for 10h at constant temperature, and finally cooling to room temperature to obtain the alpha-alumina carrier. The alpha-alumina carrier prepared in example 4 was designated as Scar-4, and the data on the relevant physical properties are shown in Table 2.
(2) Preparation of the catalyst:
the preparation method of the silver catalyst in example 1 was the same, except that the alpha-alumina support was modified correspondingly to the scara-4 numbered alpha-alumina support prepared in example 4.
(3) Evaluation of catalytic performance of silver catalyst:
the activity and selectivity of the catalyst at various stages were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
Comparative example 1
(1) Preparation of the carrier:
weighing 360.0g of gibbsite, 240.0g of pseudo-boehmite, 8.0g of ammonium fluoride and 5.0g of barium sulfate, putting the gibbsite, mixing the materials uniformly in a mixer, transferring the mixer into a kneader, adding dilute nitric acid (nitric acid: water: 1: 3, volume ratio) until the materials are kneaded into paste which can be extruded and formed, putting the paste into a strip extruder, extruding the paste into a seven-hole column, drying the seven-hole column for more than 24h at the temperature of between 60 and 120 ℃ to reduce the free water content to below 10 percent, then putting the dried seven-hole column into a natural gas kiln for roasting, wherein the roasting temperature is 1350 ℃, roasting the seven-hole column at constant temperature for 10h, and finally cooling the seven-hole column to room temperature to obtain the alpha-alumina carrier. The alpha-alumina support prepared in comparative example 1 was identified as Ccar-1 and the relevant physical property data are shown in table 2.
(2) Preparation of silver catalyst:
the preparation of the silver catalyst was the same as in example 1 except that the alpha-alumina support was modified correspondingly to the Ccar-1 numbered alpha-alumina support prepared in comparative example 1.
(3) Evaluation of catalytic performance of silver catalyst:
the activity and selectivity of the catalyst at various stages were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
Comparative example 2
(1) Preparation of the carrier:
460.0g of gibbsite, 240.0g of pseudo-boehmite, 8.0g of ammonium fluoride and 5.0g of barium sulfate are weighed and put into a mixer to be uniformly mixed, the mixer is transferred into a kneader, dilute nitric acid (nitric acid: water: 1: 3, volume ratio) is added until the mixture is kneaded into paste which can be extruded and formed, the paste is put into a strip extruder to be extruded into a seven-hole column, the seven-hole column is dried for more than 24h at the temperature of 60-120 ℃ to reduce the free water content to below 10 percent, then the dried seven-hole column is put into a natural gas kiln to be calcined, the calcining temperature is 1350 ℃, the constant temperature calcining is carried out for 10h, and finally the mixture is cooled to room temperature to obtain the alpha-alumina carrier. The alpha-alumina support prepared in comparative example 1 was identified as Ccar-2 and the relevant physical property data are shown in table 2.
(2) Preparation of silver catalyst:
the preparation of the silver catalyst was the same as in example 1 except that the alpha-alumina support was modified correspondingly to the Ccar-2 numbered alpha-alumina support prepared in comparative example 1.
(3) Evaluation of catalytic performance of silver catalyst:
the activity and selectivity of the catalyst at various stages were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
TABLE 2
| Carrier numbering | Specific surface area (m)2/g) | Crush strength (N/grain) | Water absorption (%) |
| Scar-1 | 1.41 | 130 | 50.9 |
| Scar-2 | 1.47 | 129 | 52.1 |
| Scar-3 | 1.59 | 120 | 50.3 |
| Scar-4 | 1.28 | 207 | 50.7 |
| Ccar-1 | 1.32 | 139 | 50.1 |
| Ccar-2 | 1.29 | 119 | 50.4 |
TABLE 3
As can be seen by comparing the data in tables 2 and 3, the alpha-alumina carrier is prepared by adopting the composite-phase alumina to replace a pore-forming agent and a plurality of expensive auxiliary agents in the preparation process of the carrier, and the silver catalyst prepared by the carrier has good selectivity and stability in the ethylene epoxidation reaction, and the activity is not reduced.
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, within the scope of the claims and without departing from the scope and spirit of the invention.
Claims (11)
1. An alpha-alumina carrier, characterized in that the alpha-alumina carrier is prepared by a method comprising the steps of:
step S1, preparing a solid powder having the following composition: mixing the solid powder with a binder and water to obtain a mixture;
the composite phase alumina comprises at least two of gamma-alumina, theta-alumina, kappa-alumina, eta-alumina and alpha-alumina; the composite phase alumina is obtained by roasting aluminum hydroxide at the temperature of 750-1100 ℃; the aluminum hydroxide is gibbsite and/or bayerite;
step S2, molding the mixture obtained in the step S1 to obtain a molded body;
step S3, drying and roasting the formed body obtained in the step S2 to obtain the alpha-alumina carrier;
the alpha-alumina carrier has a spheroidal appearance.
2. The alpha-alumina support as claimed in claim 1, wherein the composite phase alumina is present in an amount of 1 to 70 wt%, the pseudoboehmite is present in an amount of 20 to 50 wt%, the alkaline earth metal compound is present in an amount of 0.1 to 5 wt%, and the fluorine-containing compound is present in an amount of 0 to 3 wt%, based on the total weight of the solid powder; the weight ratio of the alumina trihydrate to the pseudo-boehmite is 0-4: 1; the weight ratio of the binder to the water is 1: 1-10; the weight ratio of the total weight of the binder and the water to the solid powder is 1: 2-10.
3. An alpha-alumina support according to claim 1, wherein the alkaline earth metal compound is selected from one or more of the oxides, nitrates, acetates, oxalates and sulfates of strontium and/or barium.
4. The alpha-alumina support of claim 1, wherein the alumina trihydrate is selected from one or more of nordstrandite, gibbsite, and bayerite.
5. The alpha-alumina support according to claim 1, wherein the fluorine-containing compound is selected from one or more of ammonium fluoride, magnesium fluoride and lithium fluoride.
6. The alpha-alumina support according to claim 1, wherein the binder is selected from one or more of citric acid, nitric acid, hydrochloric acid, formic acid and acetic acid.
7. The α -alumina support according to claim 1, wherein the α -alumina support has the following characteristics: the alpha-alumina component accounts for more than or equal to 98 percent of the total weight of the carrier, and the specific surface area is 0.5-3.5m2The pore volume is 0.3-1.0mL/g, the most probable pore diameter is 0.1-30.0 μm, the water absorption is more than or equal to 40%, and the crushing strength is 30-400N/grain.
8. A silver catalyst for olefin epoxidation, the silver catalyst comprising a carrier and an active component silver supported on the carrier, characterized in that the carrier is an α -alumina carrier as claimed in any one of claims 1 to 7.
9. The silver catalyst for olefin epoxidation according to claim 8, wherein said silver catalyst further comprises:
alkali metal and/or alkaline earth metal, or, an alkali metal-based compound and/or an alkaline earth metal-based compound;
rhenium metal and/or rhenium-based compounds; and
optionally, a rhenium co-promoter element selected from one or more of cerium, sulfur, molybdenum, chromium, or oxyanions in the form of their salts or acids.
10. A process for the epoxidation of an olefin, which process comprises subjecting an olefin to olefin epoxidation reaction in the presence of a silver catalyst as claimed in claim 8 or 9 to obtain an epoxy compound.
11. The olefin epoxidation process of claim 10, wherein said olefin is selected from one or more of styrene, propylene, ethylene, and 1, 3-butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710832849.9A CN109499558B (en) | 2017-09-15 | 2017-09-15 | Alpha-alumina carrier, silver catalyst and olefin epoxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710832849.9A CN109499558B (en) | 2017-09-15 | 2017-09-15 | Alpha-alumina carrier, silver catalyst and olefin epoxidation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109499558A CN109499558A (en) | 2019-03-22 |
| CN109499558B true CN109499558B (en) | 2021-09-21 |
Family
ID=65744934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710832849.9A Active CN109499558B (en) | 2017-09-15 | 2017-09-15 | Alpha-alumina carrier, silver catalyst and olefin epoxidation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109499558B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230256420A1 (en) * | 2020-06-26 | 2023-08-17 | Basf Se | Shaped catalyst body for the production of ethylene oxide |
| WO2021260140A1 (en) * | 2020-06-26 | 2021-12-30 | Basf Se | Production of porous alpha-alumina supports from boehmitic derived aluminas |
| EP4171801A1 (en) * | 2020-06-26 | 2023-05-03 | Basf Se | Tableted alpha-alumina catalyst support |
| CN115867381A (en) * | 2020-06-26 | 2023-03-28 | 巴斯夫欧洲公司 | Shaped porous catalyst support bodies |
| CN114425373B (en) * | 2020-09-25 | 2023-09-08 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN114433045B (en) * | 2020-11-05 | 2023-07-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| EP4359123A1 (en) * | 2021-06-25 | 2024-05-01 | Basf Se | High purity tableted alpha-alumina catalyst support |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046317A1 (en) * | 1996-06-05 | 1997-12-11 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst and process |
| CN103769233A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst |
| CN104039705A (en) * | 2011-12-20 | 2014-09-10 | Ifp新能源公司 | Method for manufacturing spheroidal alumina particles |
| CN108607618A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of alumina support, the silver catalyst prepared by the carrier and its application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1838990A (en) * | 2003-08-22 | 2006-09-27 | 联合碳化化学及塑料技术公司 | Modified alumina carriers and silver-based catalysts for the production of alkylene oxides |
| CN106955693B (en) * | 2016-01-08 | 2022-08-19 | 中国石油化工股份有限公司 | Alpha-alumina carrier of silver catalyst for ethylene epoxidation as well as preparation and application thereof |
-
2017
- 2017-09-15 CN CN201710832849.9A patent/CN109499558B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046317A1 (en) * | 1996-06-05 | 1997-12-11 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst and process |
| CN104039705A (en) * | 2011-12-20 | 2014-09-10 | Ifp新能源公司 | Method for manufacturing spheroidal alumina particles |
| CN103769233A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst |
| CN108607618A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of alumina support, the silver catalyst prepared by the carrier and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109499558A (en) | 2019-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109499558B (en) | Alpha-alumina carrier, silver catalyst and olefin epoxidation method | |
| TWI547313B (en) | A silver catalyst carrier, a process for its preparation, a silver catalyst made from the carrier and a use thereof | |
| CN102397795B (en) | Silver catalyst carrier for ethylene oxide production, preparation method, silver catalyst prepared by silver catalyst carrier, and application thereof | |
| KR101698945B1 (en) | An alumina support, a preparation method for the same, and a silver catalyst prepared from the same, and use thereof | |
| CA2987423A1 (en) | Method for producing porous bodies with enhanced properties | |
| JPH0256246A (en) | Production for catalyst including silver for ethylene oxide | |
| CN108283943B (en) | Alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation reaction and method for preparing ethylene oxide by ethylene epoxidation | |
| CN109499560B (en) | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method | |
| CN108607617B (en) | Method for preparing alumina carrier for silver catalyst and silver catalyst | |
| CN114433045B (en) | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method | |
| CN107812542B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN109499559B (en) | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method | |
| CN109201027B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN115364835A (en) | Modified alpha-alumina carrier, silver catalyst and application | |
| CN112007625A (en) | Alpha-alumina carrier, preparation method thereof, silver catalyst and application | |
| CN107442109B (en) | Silver catalyst carrier, preparation method and application thereof | |
| CN111437888A (en) | α -alumina carrier, silver catalyst for ethylene epoxidation and application | |
| CN108686712B (en) | Modified alpha-alumina carrier and preparation method thereof, silver catalyst and application | |
| CN111939884A (en) | Alpha-alumina carrier and preparation method thereof, silver catalyst and application | |
| CN112439399B (en) | Alpha-alumina carrier, preparation method, silver catalyst and application | |
| CN109201122B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN115475609A (en) | High-stability alpha-alumina carrier, silver catalyst and olefin epoxidation method | |
| CN112121780A (en) | Alpha-alumina carrier and preparation method thereof, silver catalyst and application | |
| CN112125869B (en) | Method for preparing ethylene oxide by ethylene epoxidation | |
| CN109107553B (en) | Alumina carrier and preparation method thereof, silver catalyst and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |