CN107442109A - A kind of silver catalyst carrier, its preparation method and application - Google Patents
A kind of silver catalyst carrier, its preparation method and application Download PDFInfo
- Publication number
- CN107442109A CN107442109A CN201610380422.5A CN201610380422A CN107442109A CN 107442109 A CN107442109 A CN 107442109A CN 201610380422 A CN201610380422 A CN 201610380422A CN 107442109 A CN107442109 A CN 107442109A
- Authority
- CN
- China
- Prior art keywords
- carrier
- silver catalyst
- compound
- rhenium
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000004332 silver Substances 0.000 title claims abstract description 105
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000003282 rhenium compounds Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 230000001404 mediated effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 41
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 36
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 229910052702 rhenium Inorganic materials 0.000 claims description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- 239000010937 tungsten Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 238000002803 maceration Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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
- 238000006735 epoxidation reaction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 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 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000012764 semi-quantitative analysis Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HDCUKDHYRMGLRT-UHFFFAOYSA-L [Ag+2].[O-]C(=O)C([O-])=O Chemical class [Ag+2].[O-]C(=O)C([O-])=O HDCUKDHYRMGLRT-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 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 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 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
- 238000012937 correction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—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
- 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
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention relates to a kind of silver catalyst carrier, its preparation method and application.The silver catalyst carrier, its surface attachment have the oxide selected from least one of manganese oxide, oxide and rheium oxide.The preparation method comprises the following steps：I. prepare comprising gibbsite, a false water aluminum oxide, fluoride-mineralization agent and can after-flame lubriation material mixture；II. the mixture and binding agent are mediated, it is dried afterwards, then it is calcined, the presoma of alumina support is obtained, III contains the compound selected from least one of tungsten compound, manganese compound and rhenium compound by the presoma dipping solution of the carrier in the solution, then separation of solid and liquid is carried out, solid phase is heat-treated afterwards, temperature is 150 750 DEG C, obtains the silver catalyst carrier.Silver catalyst prepared by the carrier that the present invention also provides has the advantages of preferably activity, selectivity and stability, and also has certain regulating power.
Description
Technical field
The present invention relates to a kind of silver catalyst carrier and preparation method thereof, and more specifically the present invention relates to one kind to produce epoxy
Silver catalyst carrier, its preparation method and the application of ethane.
Background technology
The reaction of industrial ethylene epoxidizing generation oxirane widely uses silver catalyst, while side reaction depth occurs
Oxidation generation carbon dioxide and water, the catalyst is generally using aluminum oxide as carrier, using silver as active component, while comprising certain
Auxiliary agent is to improve its catalytic performance, and its activity, selectivity and stability are three main performance indications in actual applications.It is living
Property refer to space-time yield or the reaction temperature required in the case where reaching certain space-time yield that catalyst is applicable；Be applicable when
Empty yield is higher, or required reaction temperature is lower under certain space-time yield, and the activity of silver catalyst is higher.Selectively it is
Refer to ethene in reaction and change into the ratio between the molal quantity of oxirane and the overall reaction molal quantity of ethene.Stability is then expressed as referring to
The rate of decay of catalyst activity and selectivity under certain reaction condition, the stability of fall off rate more small catalyst are better.
The performance of silver catalyst influences very big on economic benefit during ethylene produces oxirane, improves silver catalyst
Activity, selectivity and stability are the Main ways of silver catalyst research.
In order to improve the effect and efficiency that silver catalyst prepares oxirane, addition auxiliary agent is lifting silver catalyst performance
One of important means, the addition of auxiliary agent can be with the performance of significant impact catalyst, and the addition of auxiliary agent is from the list of beginning at present
One auxiliary agent develops into mating type or synergetic auxiliary agent containing Multiple components, and auxiliary component and its content in the catalyst turn into silver
The important component of catalyst research.By introducing the collaboration auxiliary agent of rhenium and rhenium in silver catalyst in US4761394, greatly
The selectivity for improving reaction of degree, it is proposed high selectivity silver catalyst of the highest selectivity more than 88%.CN1080636
It is proposed, manganese can be used as a kind of synergy salt component, auxiliary agent potassium in cooperation catalyst, and the synergy gas with being added in reaction gas into
Divide (such as oxynitrides), act to form redox reaction pair jointly, so as to greatly improve oxirane selectivity.
One kind is described in US4766105 using alkali metal, rhenium as auxiliary agent, and add the coassist agent of sulphur, molybdenum, tungsten, chromium and its mixture
Epoxy ethane silver catalyst.WO1997036680 then report in rhenium-containing epoxyethane catalyst add selected from sulphur, molybdenum,
Tungsten, chromium, phosphorus, boron and its mixture improve as the co-accelerator of rhenium to catalyst performance.CN101678332 is more detailed
It is proposed to add in rhenium-containing silver catalyst selected from sulphur, phosphorus, boron and their mixture the first co-accelerator with selected from tungsten, molybdenum,
Second co-accelerator of their mixture of chromium has the selectivity that idea improves production oxirane.It is main in above-mentioned patent document
The performance of silver catalyst is improved using adding tungsten, manganese, rhenium in silver catalyst formula, with middle high selectivity silver catalyst
Heavy industrialization application, the requirement to silver catalyst performance is also improving constantly, using appropriate method in doping and modification
Auxiliary agent improves catalyst performance and adversely not affected again.
The performance of silver catalyst also uses in addition to having important relationship with the composition of catalyst and preparation method with catalyst
The performance of carrier and its preparation have important relationship.For the alumina support used in silver catalyst, researchers generally pass through to
Microcomponent is added in carrier and changes its chemical composition, physical property than surface, aperture, pore size distribution and porosity etc. to change
It is apt to its performance, is pre-processed including the addition mode such as metal oxide or other compounds.Carried in WO1997040933
The oxide of zirconium, titanium, silicon and alkaline-earth metal (calcium, magnesium, strontium) is added in body.CN1467022 is the activity for improving catalyst, right
The carrier obtained after high-temperature roasting has carried out water washing alkali process, including the use of two kinds of processing sides of alkaline substance solution or gas
Formula, alkaline matter dosage is using vehicle weight percentages as 0.01-500%, and 30-800 DEG C for the treatment of temperature, processing time, 1-30 was small
When, the carrier after water washing alkali process, it is neutrality to efflux, dries, obtain silver catalyst carrier, alkali cleaning have adjusted carrier table
Face and the microcellular structure of inside, make carrier surface produce more highenergy sites, so that being supported on these highenergy sites
Silver and co-catalyst ratio generally show higher reactivity, the silver catalyst performance for making to be prepared by the silver catalyst carrier has
Significantly improve.In US5929259 by the carrier impregnation baked in the liquid phase containing titanium dioxide, the two of generation is then calcined
Titanium oxide is dispersed in the carrier, and then catalyst is made with alkali metal in load silver, improves the initial activity of silver catalyst
And selectivity.CN1400048 handles alpha-alumina supports with the sol impregnation containing cerium or zirconium, then load silver and co-catalyst system
Standby silver catalyst, to solve the extension with the reaction time, the silver granuel in catalyst is easily assembled, and causes silver catalyst inadequate
The problem of the problem of stable or catalyst activity are not high enough, activity, selectivity and the stability of catalyst are obtained for different journeys
The raising of degree.
Although above-mentioned patent document is square using different auxiliary agent etc. is added in the carrier in alumina raw material or after calcining
Method improves alumina support, brings different degrees of improvement to the activity, selectivity and stability of catalyst, but how more to pass through
The facilitation for having given play to corresponding additive of Ji, the performance of silver catalyst, especially stability are further improved, is researchers
One of focus on research direction.
The content of the invention
According to the deficiencies in the prior art, the invention provides a kind of silver catalyst carrier and preparation method thereof, the silver
Carriers for catalysts, crushing strength is high and specific surface area is big, the silver catalyst prepared using the carrier, and catalytic performance is high, stably
Property is good, disclosure satisfy that the commercial Application demand prepared needed for silver catalyst, and has certain regulating power, can improve silver on demand
The stability of catalyst or other performances.
According to an aspect of the invention, there is provided a kind of silver catalyst carrier, its surface attachment have selected from manganese oxide,
The oxide of at least one of oxide and rheium oxide.
Carrier according to the present invention, the oxide of formation add coarse structure in smooth oxidation aluminium surface,
The specific surface area of carrier surface is increased, and carrier inside crystal structure will not be destroyed to reduce the intensity of carrier, is also not in
The outer surface of Argent grain in silver catalyst.In the catalyst subsequently prepared, the tungsten, manganese and/or rhenium play a role (to
The growth of Argent grain provides site) while, the avtive spot on silver catalyst surface Argent grain surface will not be sacrificed.
According to the present invention, modification tungsten, manganese and rhenium rear bearing body surface face color are different, when W content is more based on yellow, manganese
It is in light yellowish brown when content is more based on brown, when rhenium content is more；Carrier inside section color is still white.
According to the specific embodiment of the present invention, using silver catalyst carrier as gross mass, the matter of tungsten (referring to wolfram element)
Amount content is below 2000ppm, such as 100-2000ppm；And/or the mass content of manganese (referring to violent element) is below 2000ppm, such as
100-2000ppm；And/or the mass content of rhenium (referring to rhenium element) is below 2000ppm, such as 100-2000ppm.
According to the present invention, resulting alumina support crystal formation is based on α types.The load prepared using the method for the invention
Body, crushing strength is high, and specific surface area is big, and according to the specific embodiment of the present invention, the crushing strength of the carrier is 30-
200N/ grains, preferably 60-160N/ grains, specific surface area 0.3-3m2/ g, preferably 1.6-2.5m2/g。
According to silver catalyst carrier provided by the invention, when further introducing silvery on carrier for silver catalyst,
Silver granuel nucleating growth on the site of tungstenic and/or manganese and/or rhenium, makes silver be more evenly distributed to a certain degree, is advantageous to improve and lives
Property, stability and selectivity.
According to an aspect of the present invention, there is provided a kind of preparation method of silver catalyst carrier, comprise the following steps：
I. prepare comprising gibbsite, a false water aluminum oxide, fluoride-mineralization agent and can after-flame lubriation material mixing
Thing；
II. the mixture and binding agent are mediated, is dried, is then calcined afterwards, before obtaining alumina support
Drive body；
III. the presoma dipping of the carrier is contained in the solution, in the solution and closed selected from tungsten compound, manganese
The compound of at least one of thing and rhenium compound, then carries out separation of solid and liquid, solid phase is heat-treated afterwards, temperature is
150-750 DEG C, obtain the silver catalyst carrier.
According to method of the present invention, tungsten compound and/or manganese compound and/or rhenium compound are made after Overheating Treatment
Carrier surface is attached to for oxide, increases crushing strength and specific surface area；And carrier inside crystal structure will not be destroyed, no
The intensity of carrier can be destroyed.The silver catalyst prepared using the carrier, while promoter effect is given full play to, will not also sacrifice
The avtive spot on catalyst surface Argent grain surface, and then the catalytic performance of catalyst is high, stability is good.
According to method of the present invention, the gibbsite is original conventional in the art with a false water aluminum oxide
Material, its parameter such as mesh number etc. are conventional parameters, and here is omitted.For example, gibbsite be selected from α-gibbsite and
At least one of β-gibbsite.According to a particular embodiment of the invention, the gibbsite is selected from α-three water oxygens
At least one of aluminium and β-gibbsite.According to the specific embodiment of the present invention, the gibbsite and vacation one
The mass ratio of water aluminum oxide is (0.5-4):1.
According to the present invention, the addition of the fluoride-mineralization thing can substantially speed up the transformation of crystal of aluminum oxide, change and carry
The configuration of surface of body, reduce the formation of the aperture below 0.1 μm of aperture, beneficial to follow-up tungsten, manganese, the modification of rhenium and silver catalyst
Preparation.According to the specific embodiment of the present invention, the fluoride for example may be selected from ammonium fluoride, aluminum fluoride and potassium fluoride
At least one, preferred fluorinated ammonium.
According to the present invention, it is described can after-flame lubriation material be added to increase macropore ratio shared in total pore size distribution
Weight, suitable pore structure is provided and than surface for the attachment of follow-up tungsten, manganese, rhenium.Can after-flame lubrication in follow-up roasting process
Material complete oxidation, generation gas effusion, forms the larger duct in aperture in the carrier.According to another specific reality of the present invention
Apply example, it is described can after-flame lubriation material for example may be selected from least one of petroleum coke, graphite and vaseline, preferably petroleum coke.
According to another specific embodiment of the present invention, in step II, the binding agent is acid solution, is preferably selected from
The aqueous solution of at least one of nitric acid, acetic acid and citric acid.Acid mixed with water before volume ratio 1:10 to 1:Between 1.Institute
The dosage for stating binding agent is the 10-80wt% based on the total weight of the mixture, preferably 20-50wt%.
According to the present invention, the method known to those skilled in the art that can be selected of mediating is carried out, and is carried out preferably in kneader,
Time is 10-100min.According to the present invention, the shaping can be selected method known to those skilled in the art and carry out, and preferably be molded
Carried out in machine, solid shape is single hole or seven apertures in the human head column after shaping.According to the present invention, those skilled in the art can be selected in the drying
Known method is carried out, and is preferably carried out in an oven, and drying temperature is 40-110 DEG C, time 24-72h.
According to the present invention, the crystal formation of the presoma of the alumina support is essentially α types after the roasting, according to this
Another specific embodiment of invention, the sintering temperature are 1200-1500 DEG C, and roasting time is 2-30 hours, heating rate
For 2-100 DEG C/min.
In the solution, the concentration of the tungsten compound is below 2wt%, preferably 0.01-2wt%, more preferably 0.01-
1wt%.The concentration of the manganese compound is below 2wt%, preferably 0.01-2wt%, more preferably 0.01-1wt%.The rhenium
The concentration of compound is below 2wt%, preferably 0.01-2wt%.
According to the present invention a specific embodiment, in the step III, in the solution, the tungsten compound
Selected from ammonium metatungstate, sodium tungstate and potassium tungstate.The concentration of the tungsten compound is below 2wt%, preferably 0.01-2wt%, more excellent
Elect 0.01-1wt% as.The manganese compound is selected from least one of potassium permanganate, potassium acetate and potassium sulfate.The manganese is closed
The concentration of thing is below 2wt%, preferably 0.01-2wt%, more preferably 0.01-1wt%.The rhenium compound is selected from high rhenium
At least one of sour potassium, rehenic acid ammonium and perrhenic acid.The concentration of the rhenium compound is below 2wt%, preferably 0.01-2wt%.
Process in accordance with the present invention III, impregnate fully infiltrated without tiny bubble, surfaces externally and internally to carrier surface and be
Preferably.The amount of solution is enough to submerge the carrier.In a specific embodiment, the dip time is 10-300 minutes.Together
When, the support precursor helps to wash away the solid powder and soluble impurity of surface residual after roasting with solution dipping
And block the dust in space.Separation of solid and liquid is carried out afterwards, and specific method can take filtering or directly pour out liquid phase part, protect
Stay the liquid that the surface of solids adsorbs naturally.
According to the present invention, in step III, the tungsten, manganese and/or rhenium compound are converted into respective oxygen after being thermally decomposed
Compound is adhered in carrier surface, and the oxide of formation adds coarse structure in smooth oxidation aluminium surface, increases carrier
The specific surface area on surface, and the intensity of carrier inside crystal structure reduction carrier will not be destroyed, do not appear in silver catalyst yet
The outer surface of middle Argent grain.In the catalyst subsequently prepared, the tungsten, manganese and/or rhenium will not be sacrificial while playing a role
The avtive spot on domestic animal silver catalyst surface Argent grain surface.
According to another specific embodiment of the present invention, the heat treatment temperature is 300-700 DEG C, such as 300-600 DEG C,
300-400 DEG C, 300-500 DEG C.During heat treatment, heating rate can be 2-100 DEG C/min.The heat treatment can in air or
Carried out in inert gas such as nitrogen, argon gas atmosphere.The time of the heat treatment is 1-600 minutes, preferably 1-60 minutes.
According to the present invention, modification tungsten, manganese and rhenium rear bearing body surface face color can change, when W content is more using yellow as
It is main, it is in light yellowish brown when manganese content is more based on brown, when rhenium content is more；Carrier inside section color is still white.
According to the specific embodiment of the present invention, using silver catalyst carrier as gross mass, the mass content of tungsten is
Below 2000ppm, such as 100-2000ppm；And/or the mass content of manganese is below 2000ppm, such as 100-2000ppm；And/or
The mass content of rhenium is below 2000ppm, such as 100-2000ppm.
According to the present invention, resulting alumina support crystal formation is based on α types.The load prepared using the method for the invention
Body, crushing strength is high, and specific surface area is big, and according to the specific embodiment of the present invention, the crushing strength of the carrier is 30-
200N/ grains, preferably 60-160N/ grains, specific surface area 0.3-3m2/ g, preferably 1.6-2.5m2/g。
According to another aspect of the present invention, a kind of preparation method of silver catalyst is additionally provided, uses the system of the present invention
Silver catalyst carrier prepared by Preparation Method, it is excellent according to known to people in the art or conventional publicity pattern prepares silver catalyst
Choosing by the above method prepare carrier impregnation including Ag-containing compound, organic amine maceration extract in, afterwards separate, activate obtain
The silver catalyst.In a specific embodiment, the preparation method of the silver catalyst includes：(1) first according to above-mentioned side
Silver catalyst carrier prepared by method；(2) by the carrier impregnation obtained in the step (1) including Ag-containing compound and organic
In the maceration extract of amine, separation of solid and liquid is carried out afterwards, and solid phase is activated to obtain the silver catalyst.
According to the preparation method of silver catalyst provided by the invention, silver is further introduced on carrier, prepares silver catalyst
When, silver granuel nucleating growth on the site of tungstenic and/or manganese and/or rhenium, silver is more evenly distributed to a certain degree, and make final silver
Catalyst color is in silver-colored black, identical with without the silver catalyst appearance color prepared by tungsten, manganese and rhenium pre-treatment.
According to the present invention, can be carried out in the step (2) according to the step of routine.Prepared by the method in the present invention
Silver catalyst, Argent grain distribution is than more uniform, and few adhesion, the activity of unit silver is high, be advantageous to improve the selectivity of catalyst,
Activity and stability.
In a specific example, in the step (2), alkali metal promoter and/or alkali are included in the maceration extract
Earth metal auxiliary agent and/or rhenium auxiliary agent；When rhenium-containing auxiliary agent in the maceration extract, the coassist agent of rhenium auxiliary agent is also optionally included.
Catalyst according to the invention, pass through step (2), based on the gross weight of the catalyst, silver-colored load capacity 10-
30%；And/or the load capacity 5-2000ppm of alkali metal；And/or the load capacity of alkaline-earth metal is 1-1000ppm, and/or rhenium 5-
2000ppm.When rhenium-containing element, the coassist agent element of rhenium is optionally included in catalyst, its content is also 5-2000ppm.
According to another aspect of the present invention, a kind of olefin epoxidation process is additionally provided, including：First with above-mentioned side
Method prepares silver catalyst, then carries out epoxidation reaction of olefines in the presence of silver catalyst.
Method in the present invention, because the activity of silver catalyst is high, stability is good and stability is good, methods described
Cost is low, reaction efficiency is high, has high economic benefit and social benefit.
In a specific example, the alkene is ethene, and oxirane is obtained after epoxidation reaction.
According to the present invention, using the silver catalyst carrier made by the preparation method of the present invention, crushing strength is high and compares
Surface area is big, the silver catalyst prepared using the carrier, and catalytic performance is high, stability is good, and satisfaction is prepared needed for silver catalyst
Commercial Application demand, and there is certain regulating power, the stability or other performances of silver catalyst can be improved on demand.Pass through
Silver catalyst prepared by the method in the present invention, Argent grain distribution is than more uniform, and few adhesion, the activity of unit silver is high, is advantageous to
Improve selectivity, activity and the stability of catalyst.
Embodiment
Technical scheme is described further with reference to embodiment, but not formed to any of the present invention
Limitation.
(1) using the crushing strength of intelligent detector for strength of particles measure carrier；
(2) using the specific surface area of NOVA2000e specific surface instruments measure carrier；
(3) content of material being attached to using X-ray fluorescence spectra measure on carrier；
(4) using following instrument and the indices of method measure catalyst：
The present invention is using miniature tubular reactor (hereinafter referred to as " micro- anti-") evaluation initial catalyst reactivity worth and stability.
Its tubular reactor used is internal diameter 4mm stainless steel reaction pipe, and reaction tube is placed in copper or aluminum heating mantle.Silver catalysis
Agent takes catalyst granules 0.8g of the size between 12-18 mesh to be packed into reactor compacting in sieve after pulverizing, and reactor lower part has
Inert filler makes beds be located in the flat-temperature zone of heating mantle.
The catalytic activity and the standard appreciation condition of selectivity that the present invention uses are as follows：
Carry out the gas composition (mol%) of the reaction inlet of catalytic reaction：Ethene, 29.0 ± 1.0；Oxygen, 7.3 ± 0.2；
Carbon dioxide,<3.0；Nitrogen, surplus；Dichloroethanes, 0.1-2.0ppm.Reaction pressure 2.1MPa；Air speed 6000h-1；Reactor
Export the concentration 2.5% of tail gas ethylene oxide.
Be gradually heated up reactor from room temperature, when stable reaction in the operating condition after, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and go out
Gas forms.Measurement result calculates selectivity (S) as follows after carrying out volume contraction correction：
Wherein Δ EO is the concentration difference of reactor outlet gas and inlet gas ethylene oxide, and Δ CO2 is reactor outlet gas
With the concentration difference of carbon dioxide in inlet gas.
Embodiment 1
The preparation of carrier
By the gibbsite 359g of 50 mesh, the vacation of 200 mesh one water aluminum oxide 120g, ammonium fluoride 11g are put into blender
It is well mixed, it is transferred in kneader, adds 50g petroleum cokes and 20wt% dust technology 190ml, be then fully kneaded into extrudable
The cream solid of shaping.Extrusion molding is external diameter 8mm, long 8mm, (seven parallel channels sizes are respectively center to seven apertures in the human head column
Hole 1.7mm, periphery hole 1.5mm), dry more than 24 hours at 90-100 DEG C, then the carrier of shaping is put into kiln, pass through
1300 DEG C are increased to from room temperature, and is calcined 6 hours under the conditions of 1300 DEG C within 40 hours, obtain white alumina support precursor.
Prepare a certain amount of solution for standby, wherein ammonium metatungstate concentration 0.05wt%, manganese acetate concentration 0.10wt%, rehenic acid
Ammonium concentration 0.10wt%.Support precursor 311g is weighed, is totally submerged in ready solution, decompression dipping 20 minutes, mistake
Elimination removes unnecessary solution.Carrier after dipping heats 3min under 700 DEG C of air atmosphere, and cooling obtains the carrier production of brown
Product.
The preparation of catalyst
49.1g ethylenediamines and 12.7g monoethanolamines are dissolved in 100g deionized waters, under agitation delayed 105.3g silver oxalates
Slow to add in mixed liquor, temperature is maintained at less than 40 DEG C, silver oxalate is all dissolved, it is high to add 0.24g cesium nitrates, 0.11g
Rehenic acid amine, it is stand-by to be configured to maceration extract after well mixed.
Support samples 30g is taken, is put into the container that can be vacuumized, vacuumizing makes pressure be down to below 10mmHg, in addition
State maceration extract to liquid level and be totally submerged solid, kept for 30 minutes, leaching removes unnecessary solution.Carrier after dipping is at 260 DEG C
Air stream in heat 3 minutes, cool down, that is, silver catalyst is made.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
The semi-quantitative analysis result of auxiliary agent content on carrier is shown in Table 2 below, and will obtain silver using microreactor evaluating apparatus urges
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Embodiment 2
The preparation of carrier is with embodiment 1, and difference is that heat treatment temperature is 300 DEG C, and the preparation of catalyst is the same as implementation
Example 1.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
The semi-quantitative analysis result of auxiliary agent content on carrier is shown in Table 2 below, and will obtain silver using microreactor evaluating apparatus urges
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Embodiment 3
With embodiment 1, difference is that the formula of solution is changed to 0.10wt% ammonium metatungstate, does not have for the preparation of carrier
Add manganese acetate and rehenic acid ammonium.The preparation of catalyst is the same as embodiment 1.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
The semi-quantitative analysis result of auxiliary agent content on carrier is shown in Table 2 below, and will obtain silver using microreactor evaluating apparatus urges
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Embodiment 4
With embodiment 1, difference is that the formula of solution is changed to 0.10wt% manganese acetate for the preparation of carrier, does not add
Enter ammonium metatungstate and rehenic acid ammonium.The preparation of catalyst is the same as embodiment 1.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
The semi-quantitative analysis result of auxiliary agent content on carrier is shown in Table 2 below, and will obtain silver using microreactor evaluating apparatus urges
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Embodiment 5
With embodiment 1, difference is that the formula of solution is changed to 0.10wt% rehenic acid ammonium for the preparation of carrier, does not add
Enter manganese acetate and ammonium metatungstate.The preparation of catalyst is the same as embodiment 1.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
The semi-quantitative analysis result of auxiliary agent content on carrier is shown in Table 2 below, and will obtain silver using microreactor evaluating apparatus urges
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Comparative example 1
With embodiment 1, difference is not handle support precursor with maceration extract for the preparation of carrier.The system of catalyst
For with embodiment 1.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
During the semi-quantitative analysis result content of auxiliary agent on carrier is shown in Table 2 below, it will obtain silver using microreactor evaluating apparatus and urge
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Comparative example 2
With embodiment 1, difference is not handle support precursor with maceration extract for the preparation of carrier.The system of catalyst
Standby process adds following material again on the basis of embodiment 1 in maceration extract：Ammonium metatungstate concentration 0.05wt%, manganese acetate concentration
0.10wt% and rehenic acid ammonium concentration 0.10wt%, concentration are based on maceration extract.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
During the semi-quantitative analysis result content of auxiliary agent on carrier is shown in Table 2 below, it will obtain silver using microreactor evaluating apparatus and urge
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Comparative example 3
The preparation of carrier is the same as comparative example 2.The preparation process of catalyst is added partially on the basis of embodiment 1 in maceration extract
Ammonium tungstate, its concentration are 0.10wt%.
Carrier is tested, test result is shown in Table 1 below, because each auxiliary agent content is extremely low, it is difficult to accurate detection, will
During the semi-quantitative analysis result content of auxiliary agent on carrier is shown in Table 2 below, it will obtain silver using microreactor evaluating apparatus and urge
Agent is evaluated one month according to foregoing evaluation method, and experimental result is included in table 3.
Find out in table 1, compared to comparative example 1, use heretofore described preparation method, the carrier crushing strength of preparation
Height, specific surface area are big.
It can be seen from the data in Table 3 that the data in embodiment 1 and comparative example 1 and 2 are contrasted, the present invention is used
Described in preparation method prepare carrier silver catalyst, catalytic performance is good, and especially reaction temperature is held essentially constant, surely
It is qualitative to be greatly improved, improve selectivity.Embodiment 3 and comparative example 3 are contrasted, using the side in the present invention
Method, reaction temperature is not only greatly reduced, improve catalyst activity, also improve selectivity and stability.
Table 1
| Crushing strength (N/ grains) | Specific surface area (m2/g) | |
| Embodiment 1 | 92 | 1.66 |
| Embodiment 2 | 85 | 1.79 |
| Embodiment 3 | 60 | 1.73 |
| Embodiment 4 | 76 | 1.72 |
| Embodiment 5 | 89 | 1.69 |
| Comparative example 1 | 76 | 1.56 |
| Comparative example 2 | 76 | 1.56 |
| Comparative example 3 | 76 | 1.56 |
Table 2
| Tungsten (wt%) | Manganese (wt%) | Rhenium (wt%) | |
| Embodiment 1 | 0.03 | 0.05 | 0.03 |
| Embodiment 2 | 0.03 | 0.05 | 0.05 |
| Embodiment 3 | 0.05 | 0.00 | 0.005 |
| Embodiment 4 | 0.00 | 0.05 | 0.00 |
| Embodiment 5 | 0.00 | 0.00 | 0.02 |
| Comparative example 1 | 0.00 | 0.00 | 0.00 |
| Comparative example 2 | 0.00 | 0.00 | 0.00 |
| Comparative example 3 | 0.00 | 0.00 | 0.00 |
Table 3
From the contrast of data it is known that using method provided by the invention, Argent grain distribution is than more uniform, few adhesion,
While tungsten and/or violent and/or rhenium effect is played, the avtive spot in catalyst Argent grain surface can will not be sacrificed,
Improve the selectivity, activity and stability of silver catalyst.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (14)
1. a kind of silver catalyst carrier, its surface attachment have selected from least one of manganese oxide, oxide and rheium oxide
Oxide.
2. carrier according to claim 1, it is characterised in that the gross weight based on the carrier, the quality of wolfram element contain
Measure as below 2000ppm；And/or the mass content of manganese element is below 2000ppm；And/or the mass content of rhenium element is
Below 2000ppm.
3. a kind of preparation method of silver catalyst carrier, comprises the following steps：
I. prepare comprising gibbsite, a false water aluminum oxide, fluoride-mineralization agent and can after-flame lubriation material mixture；
II. the mixture and binding agent are mediated, is dried, is then calcined afterwards, obtain the presoma of alumina support；
III. by the presoma of carrier dipping in the solution, contain in the solution selected from tungsten compound, manganese compound and
The compound of at least one of rhenium compound, separation of solid and liquid is then carried out, solid phase is heat-treated afterwards, the temperature of heat treatment
For 150-750 DEG C, the silver catalyst carrier is obtained.
4. according to the method for claim 3, it is characterised in that in the step III, the temperature of the heat treatment is
300-700℃；And/or the time of the heat treatment is 1-600 minutes, preferably 1-30 minutes.
5. the method according to claim 3 or 4, it is characterised in that in the step III, in the solution, the tungsten
The concentration of compound is below 2wt%, preferably 0.01-2wt%, more preferably 0.01-1wt%；And/or the manganese compound
Concentration is below 2wt%, preferably 0.01-2wt%, more preferably 0.01-1wt%；And/or the concentration of the rhenium compound is
Below 2wt%, preferably 0.01-2wt%.
6. according to the method described in any one in claim 3-5, it is characterised in that described tungsten compound is selected from metatungstic acid
At least one of ammonium, sodium tungstate and potassium tungstate；With or the manganese compound in potassium permanganate, potassium acetate and potassium sulfate
At least one；With or the rhenium compound be selected from least one of potassium perrhenate, rehenic acid ammonium and perrhenic acid.
7. according to the method described in any one in claim 3-6, it is characterised in that the gibbsite and a false water oxygen
The mass ratio for changing aluminium is (0.5-4)：1, and/or
The gibbsite is selected from least one of α-gibbsite and β-gibbsite；And/or the fluoride
Selected from least one of ammonium fluoride, aluminum fluoride and potassium fluoride；And/or it is described can after-flame lubriation material be selected from petroleum coke, graphite
And at least one of vaseline.
8. according to the method described in any one in claim 3-7, it is characterised in that the bonding agent is acid solution, preferably
Selected from least one of nitric acid, acetic acid and aqueous citric acid solution；And/or acid mixes front volume ratio with water 1:10 to 1:1
Between；And/or the dosage of the binding agent is the 10-80wt% of the gross weight of the mixture.
9. according to the method described in any one in claim 3-8, it is characterised in that the drying temperature is 40-110 DEG C,
Drying time is 24-72 hours；And/or the sintering temperature is 1200-1500 DEG C, the roasting time is 2-30 hours.
10. according to the method described in any one in claim 3-9, it is characterised in that the pressure of the silver catalyst carrier
Broken intensity is 30-200N/ grains, preferably 60-160N/ grains, specific surface area 0.3-3m2/ g, preferably 1.6-2.5m2/g。
11. according to the method described in any one in claim 3-10, it is characterised in that the gross mass based on the carrier,
The mass content of wolfram element is below 2000ppm；And/or the mass content of manganese element is below 2000ppm；And/or rhenium element
Mass content be below 2000ppm.
12. a kind of preparation method of silver catalyst, including：
(1) silver catalyst carrier according to claim 1 or 2, or according to any one in claim 3-11
Silver catalyst carrier prepared by method；
(2) by the carrier impregnation obtained in the step (1) in the maceration extract including Ag-containing compound and organic amine, it is laggard
Row separation of solid and liquid, solid phase is activated to obtain the silver catalyst.
13. according to the method for claim 12, it is characterised in that in the step (2), alkali is included in the maceration extract
Metal promoter and/or base earth metal promoter and/or rhenium auxiliary agent；When rhenium-containing auxiliary agent in the maceration extract, also optionally include
The coassist agent of rhenium auxiliary agent.
14. a kind of olefin epoxidation process, including：Silver catalyst is prepared using the methods described of claim 12 or 13, then
Epoxidation reaction of olefines is carried out in the presence of silver catalyst, wherein, preferably described alkene is ethene, is obtained after epoxidation reaction
Oxirane.
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| CN114425336A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Silver catalyst for producing ethylene oxide by ethylene oxidation and preparation method and application thereof |
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