CN107442109B - Silver catalyst carrier, preparation method and application thereof - Google Patents
Silver catalyst carrier, preparation method and application thereof Download PDFInfo
- Publication number
- CN107442109B CN107442109B CN201610380422.5A CN201610380422A CN107442109B CN 107442109 B CN107442109 B CN 107442109B CN 201610380422 A CN201610380422 A CN 201610380422A CN 107442109 B CN107442109 B CN 107442109B
- Authority
- CN
- China
- Prior art keywords
- carrier
- silver catalyst
- compound
- rhenium
- silver
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 115
- 239000004332 silver Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 11
- 150000003282 rhenium compounds Chemical class 0.000 claims abstract description 11
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000004684 trihydrates Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical group 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 150000004682 monohydrates Chemical class 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
- 238000004898 kneading Methods 0.000 claims abstract description 4
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910003449 rhenium oxide Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 48
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 33
- 229910052702 rhenium Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 22
- 239000010937 tungsten Substances 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000006735 epoxidation reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 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 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 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
- 238000002791 soaking Methods 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 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
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000002156 mixing Methods 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
- 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
- 239000008188 pellet Substances 0.000 claims 2
- 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 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims 1
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims 1
- 229910001930 tungsten oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 description 27
- 229910052748 manganese Inorganic materials 0.000 description 19
- 239000011572 manganese Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 10
- 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
- 239000011148 porous material Substances 0.000 description 8
- 238000012764 semi-quantitative analysis Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 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
- 239000007787 solid Substances 0.000 description 5
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 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
- 239000003513 alkali Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 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
- 239000002994 raw material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 239000012747 synergistic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
-
- B01J35/399—
-
- B01J35/612—
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a carrier for a silver catalyst, a preparation method and application thereof. The silver catalyst support has at least one oxide selected from the group consisting of manganese oxide, an oxide and rhenium oxide attached to the surface thereof. The preparation method comprises the following steps: I. preparing a mixture comprising alumina trihydrate, pseudo-alumina monohydrate, a fluoride mineralizer, and a burnout lubricant; II, kneading the mixture with a binder, drying, and then calcining to obtain a precursor of an alumina carrier, III, impregnating the precursor of the carrier into a solution containing at least one compound selected from a tungsten compound, a manganese compound, and a rhenium compound, and then carrying out solid-liquid separation, and then carrying out heat treatment on the solid phase at a temperature of 150 ℃ to 750 ℃ to obtain the carrier for the silver catalyst. The silver catalyst prepared by the carrier provided by the invention has the advantages of better activity, selectivity and stability, and also has certain regulating capability.
Description
Technical Field
The invention relates to a silver catalyst carrier and a preparation method thereof, in particular to a silver catalyst carrier for producing ethylene oxide, a preparation method and application thereof.
Background
In the industrial reaction of ethylene epoxidation to ethylene oxide, a silver catalyst is widely used, and side reactions are generated to deeply oxidize carbon dioxide and water at the same time. The activity is the space-time yield for the catalyst or the reaction temperature required to achieve a certain space-time yield; the higher the space-time yield applicable or the lower the reaction temperature required at a given space-time yield, the higher the activity of the silver catalyst. Selectivity refers to the ratio of the moles of ethylene converted to ethylene oxide in the reaction to the total moles of ethylene reacted. Stability is expressed as the rate of decay of catalyst activity and selectivity under certain reaction conditions, with lower rates of decline being better catalyst stability. The performance of the silver catalyst in the process of producing ethylene oxide by oxidizing ethylene has great influence on economic benefit, and the improvement of the activity, selectivity and stability of the silver catalyst is the main direction of the research of the silver catalyst.
In order to improve the effect and efficiency of preparing ethylene oxide by using a silver catalyst, the addition of an auxiliary agent is one of important means for improving the performance of the silver catalyst, the addition of the auxiliary agent can obviously influence the performance of the catalyst, the addition of the auxiliary agent at present is developed from a single auxiliary agent to a combined or synergistic auxiliary agent containing multiple components, and the auxiliary agent components and the content of the auxiliary agent components in the catalyst become important components for the research of the silver catalyst. In US4761394, the selectivity of reaction is greatly improved by introducing rhenium and rhenium synergistic agent into silver catalyst, and high selectivity silver catalyst with the highest selectivity over 88% is provided. CN1080636 proposes that manganese can be used as a synergistic salt component, and is matched with an auxiliary agent potassium in a catalyst, and the manganese and a synergistic gas component (such as oxynitride) added in reaction gas jointly generate action to form an oxidation-reduction reaction pair, so that the selectivity of ethylene oxide is greatly improved. US4766105 describes a silver catalyst for ethylene oxide production with alkali metals, rhenium as an adjuvant and with the addition of a co-adjuvant of sulfur, molybdenum, tungsten, chromium and mixtures thereof. WO1997036680 reports on improved catalyst performance by the addition of a co-promoter selected from the group consisting of sulfur, molybdenum, tungsten, chromium, phosphorus, boron and mixtures thereof as rhenium in a rhenium-containing ethylene oxide catalyst. CN101678332, more specifically, proposes to add a first co-promoter selected from the group consisting of sulfur, phosphorus, boron and mixtures thereof and a second co-promoter selected from the group consisting of tungsten, molybdenum, chromium and mixtures thereof to a rhenium-containing silver catalyst, with the intention of increasing the selectivity for the production of ethylene oxide. In the above patent documents, tungsten, manganese and rhenium are mainly added to the silver catalyst formula to improve the performance of the silver catalyst, and with the large-scale industrial application of the silver catalyst with medium and high selectivity, the requirements on the performance of the silver catalyst are continuously increased, and the modification assistant is doped to improve the performance of the catalyst by adopting a proper method without causing negative effects.
For alumina carriers used for silver catalysts, researchers generally modify the chemical composition, physical properties such as specific surface, pore size, pore distribution, porosity and the like of the carriers by adding trace components to the carriers to improve the performance thereof, including pretreatment by adding metal oxides or other compounds, WO1997040933 in which oxides of zirconium, titanium, silicon and alkaline earth metals (calcium, magnesium, strontium) are added to the carriers, CN1467022 is to increase the activity of the catalysts, water washing alkali treatment is performed on the carriers obtained after high temperature calcination, including both treatment with an alkaline substance solution or gas, the amount of alkaline substance is 0.01 to 500% by weight of the carriers, the treatment temperature is 30 to 800 ℃, the treatment time is 1 to 30 hours, the carriers after alkali treatment are water washed until the alumina effluent is neutral, dried to obtain silver catalyst carriers, alkali washing adjusts the surface and internal microporous structures of the carriers, makes the surface of the carriers generate more high-energy silver, the catalyst surface generates more silver, the silver-loaded catalyst-supported promoters are prepared by using high-energy catalysts, and the silver-loaded catalysts are prepared by using high-supported catalysts, thus the catalysts are prepared by using catalysts with the catalysts which are easily modified silver-supported by a high-supported catalyst-activity-supported sol, and the catalysts are prepared by calcining, and the catalysts which are not easily modified catalysts, and the catalysts which are prepared by using high-supported catalysts which are not used for high-supported by high-supported catalysts which are generally by high-activity-supported catalysts, and the catalysts which are prepared by alkaline substance solution, and the catalysts which are prepared by high-supported catalysts which are not used for the catalysts which are prepared by alkaline substance solution and the catalysts which are not used for the catalysts which are prepared by the catalysts which are not used for the catalysts.
Although the above patent documents improve the alumina carrier by adding different additives to the alumina raw material or the calcined carrier, and the like, to improve the activity, selectivity and stability of the catalyst to different degrees, it is one of the major research directions of researchers how to more economically exert the promoting effect of the corresponding additives and further improve the performance, especially the stability, of the silver catalyst.
Disclosure of Invention
According to the defects of the prior art, the invention provides the carrier for the silver catalyst and the preparation method thereof, the carrier for the silver catalyst has high crushing strength and large specific surface area, the silver catalyst prepared by the carrier has high catalytic performance and good stability, can meet the industrial application requirements for preparing the silver catalyst, has certain regulating capacity, and can improve the stability or other properties of the silver catalyst as required.
According to an aspect of the present invention, there is provided a carrier for silver catalyst having at least one oxide selected from the group consisting of manganese oxide, oxide and rhenium oxide attached to the surface thereof.
According to the carrier disclosed by the invention, the formed oxide adds a rough structure on the smooth alumina surface, the specific surface area of the carrier surface is increased, the crystal structure in the carrier is not damaged, the strength of the carrier is not reduced, and the oxide does not appear on the outer surface of silver particles in the silver catalyst. In the subsequently prepared catalyst, the tungsten, manganese and/or rhenium, while acting (providing sites for the growth of the silver particles), does not sacrifice the active sites on the surface of the silver particles on the surface of the silver catalyst.
According to the invention, the surfaces of the carriers after modifying tungsten, manganese and rhenium have different colors, when the content of tungsten is more, yellow is taken as the main color, when the content of manganese is more, brown is taken as the main color, and when the content of rhenium is more, the carrier is light yellow brown; the color of the internal section of the carrier is still white.
According to an embodiment of the present invention, the mass content of tungsten (which means tungsten element) is 2000ppm or less, such as 100-2000ppm, based on the total mass of the carrier for the silver catalyst; and/or the mass content of manganese (manganese element) is below 2000ppm, such as 100-2000 ppm; and/or the mass content of rhenium (referring to rhenium element) is below 2000ppm, such as 100-2000 ppm.
The alumina carrier prepared by the method has high crushing strength and large specific surface area, and according to one specific embodiment of the invention, the crushing strength of the carrier is 30-200N/particle, preferably 60-160N/particle, and the specific surface area is 0.3-3m2A/g, preferably from 1.6 to 2.5m2/g。
According to the carrier for the silver catalyst, when silver is further introduced on the carrier to prepare the silver catalyst, silver particles nucleate and grow on sites containing tungsten and/or manganese and/or rhenium, so that the silver is distributed more uniformly to a certain extent, and the activity, the stability and the selectivity are improved.
According to an aspect of the present invention, there is provided a method for preparing a carrier for a silver catalyst, comprising the steps of:
I. preparing a mixture comprising alumina trihydrate, pseudo-alumina monohydrate, a fluoride mineralizer, and a burnout lubricant;
II, kneading the mixture with a binder, drying, and then roasting to obtain a precursor of the alumina carrier;
and III, dipping a precursor of the carrier in a solution, wherein the solution contains at least one compound selected from a tungsten compound, a manganese compound and a rhenium compound, then carrying out solid-liquid separation, and then carrying out heat treatment on the solid phase at the temperature of 150-750 ℃ to obtain the carrier for the silver catalyst.
According to the method, the tungsten compound and/or the manganese compound and/or the rhenium compound are/is adhered to the surface of the carrier as oxides after being subjected to heat treatment, so that the crushing strength and the specific surface area are increased; and the crystal structure in the carrier can not be damaged, and the strength of the carrier can not be damaged. The silver catalyst prepared by the carrier can not sacrifice active sites on the surfaces of silver particles on the surface of the catalyst while fully playing the role of an auxiliary agent, and further has high catalytic performance and good stability.
According to the method, the alumina trihydrate and the pseudo-alumina monohydrate are raw materials commonly used in the field, and the parameters such as mesh number and the like are conventional parameters and are not described herein any more.
According to the invention, the addition of the fluoride mineralized substance can obviously accelerate the crystal form conversion of alumina, change the surface morphology of the carrier, reduce the formation of pores with the pore diameter of less than 0.1 mu m, and is beneficial to the subsequent modification of tungsten, manganese and rhenium and the preparation of a silver catalyst. According to a particular embodiment of the invention, the fluoride may be selected, for example, from at least one of ammonium fluoride, aluminium fluoride and potassium fluoride, preferably ammonium fluoride.
According to the invention, the burnout lubricating material is added to increase the proportion of macropores in the total pore distribution and provide a proper pore structure and specific surface for subsequent attachment of tungsten, manganese and rhenium. In the subsequent roasting process, the combustible lubricating material is completely oxidized, the generated gas escapes, and pore channels with larger pore diameters are formed in the carrier. According to another embodiment of the invention, the burnout-able lubricant material may be selected from at least one of petroleum coke, graphite and vaseline, preferably petroleum coke, for example.
According to another embodiment of the present invention, in step II, the binder is an acid solution, preferably an aqueous solution of at least one selected from nitric acid, acetic acid and citric acid. The volume ratio of the acid to water before mixing is between 1:10 and 1: 1. The binder is used in an amount of 10 to 80 wt%, preferably 20 to 50 wt%, based on the total weight of the mixture.
According to the invention, the kneading can be carried out by methods known to the person skilled in the art, preferably in a kneader, for a period of from 10 to 100 min. According to the invention, the shaping can be carried out by methods known to the person skilled in the art, preferably in a shaping machine, the shaped solid being in the form of a single-or seven-hole column. According to the invention, the drying can be carried out by methods known to the person skilled in the art, preferably in an oven, at a drying temperature of 40 to 110 ℃ for a period of 24 to 72 hours.
According to the invention, the crystal form of the precursor of the alumina carrier after roasting is basically α type, according to another specific embodiment of the invention, the roasting temperature is 1200-1500 ℃, the roasting time is 2-30 hours, and the heating rate is 2-100 ℃/min.
The concentration of the tungsten compound in the solution is 2 wt% or less, preferably 0.01 to 2 wt%, more preferably 0.01 to 1 wt%. The concentration of the manganese compound is 2 wt% or less, preferably 0.01 to 2 wt%, more preferably 0.01 to 1 wt%. The concentration of the rhenium compound is 2 wt% or less, preferably 0.01 to 2 wt%.
According to a specific embodiment of the present invention, in the step III, the tungsten compound is selected from the group consisting of ammonium metatungstate, sodium tungstate, and potassium tungstate in the solution. The concentration of the tungsten compound is 2 wt% or less, preferably 0.01 to 2 wt%, more preferably 0.01 to 1 wt%. The manganese compound is selected from at least one of potassium permanganate, potassium acetate and potassium sulfate. The concentration of the manganese compound is 2 wt% or less, preferably 0.01 to 2 wt%, more preferably 0.01 to 1 wt%. The rhenium compound is selected from at least one of potassium perrhenate, ammonium perrhenate and perrhenic acid. The concentration of the rhenium compound is 2 wt% or less, preferably 0.01 to 2 wt%.
According to step III of the present invention, the impregnation is preferably carried out until the surface of the carrier is sufficiently wetted with the inner and outer surfaces without fine bubbles. The amount of solution is sufficient to immerse the support. In one embodiment, the immersion time is 10 to 300 minutes. At the same time, impregnation of the carrier precursor with the solution helps to wash away solid powder and soluble impurities remaining on the surface after firing and dust blocking the voids. And then carrying out solid-liquid separation, wherein the specific method can adopt filtration or directly pouring out the liquid phase part, and reserving the liquid naturally adsorbed on the solid surface.
According to the invention, in step III, the tungsten, manganese and/or rhenium compounds are converted into respective oxides to be attached to the surface of the carrier after being heated and decomposed, and the formed oxides increase a rough structure on the smooth alumina surface, increase the specific surface area of the carrier surface, do not damage the crystal structure in the carrier to reduce the strength of the carrier, and do not appear on the outer surface of silver particles in the silver catalyst. In the subsequently prepared catalyst, the tungsten, manganese and/or rhenium functions without sacrificing the active sites on the surface of the silver particles on the surface of the silver catalyst.
According to another embodiment of the present invention, the heat treatment temperature is 300-. During heat treatment, the heating rate can be 2-100 ℃/min. The heat treatment may be performed in an atmosphere of air or an inert gas such as nitrogen, argon, or the like. The time for the heat treatment is 1 to 600 minutes, preferably 1 to 60 minutes.
According to the invention, the surface color of the carrier is changed after the modification of tungsten, manganese and rhenium, wherein yellow is mainly used when the content of tungsten is more, brown is mainly used when the content of manganese is more, and light yellow brown is formed when the content of rhenium is more; the color of the internal section of the carrier is still white.
According to a specific embodiment of the present invention, the tungsten content is 2000ppm or less, such as 100-2000ppm, based on the total mass of the carrier for the silver catalyst; and/or the mass content of manganese is less than 2000ppm, such as 100-2000 ppm; and/or the mass content of rhenium is below 2000ppm, such as 100-2000 ppm.
The alumina carrier prepared by the method has high crushing strength and large specific surface area, and according to one specific embodiment of the invention, the crushing strength of the carrier is 30-200N/particle, preferably 60-160N/particle, and the specific surface area is 0.3-3m2A/g, preferably from 1.6 to 2.5m2/g。
According to another aspect of the present invention, there is also provided a method for preparing a silver catalyst, wherein the carrier for a silver catalyst prepared by the preparation method of the present invention is used to prepare a silver catalyst according to a manner known or conventionally disclosed by a person skilled in the art, and the carrier prepared by the method is preferably immersed in an immersion liquid comprising a silver-containing compound and an organic amine, and then separated and activated to obtain the silver catalyst. In one particular embodiment, the method of preparing the silver catalyst comprises: (1) the carrier for silver catalyst prepared according to the above method; (2) and (2) soaking the carrier obtained in the step (1) in a soaking solution containing a silver-containing compound and organic amine, then carrying out solid-liquid separation, and activating a solid phase to obtain the silver catalyst.
According to the preparation method of the silver catalyst provided by the invention, silver is further introduced on the carrier, and during the preparation of the silver catalyst, silver particles nucleate and grow on sites containing tungsten and/or manganese and/or rhenium, so that the silver is distributed more uniformly to a certain extent, and the color of the final silver catalyst is silver black and is the same as the appearance color of the silver catalyst prepared without the pretreatment of tungsten, manganese and rhenium.
According to the present invention, the step (2) may be performed according to a conventional procedure. The silver catalyst prepared by the method has the advantages of uniform silver particle distribution, less adhesion, high unit silver activity and contribution to improving the selectivity, the activity and the stability of the catalyst.
In a specific example, in the step (2), the impregnation solution comprises an alkali metal auxiliary agent and/or an alkaline earth metal auxiliary agent and/or a rhenium auxiliary agent; when the impregnation liquid contains the rhenium auxiliary agent, a co-auxiliary agent of the rhenium auxiliary agent can be optionally contained.
The catalyst according to the invention is prepared by the step (2), wherein the loading amount of the silver is 10-30% based on the total weight of the catalyst; and/or the loading amount of alkali metal is 5-2000 ppm; and/or the loading of alkaline earth metal is 1-1000ppm, and/or rhenium is 5-2000 ppm. When rhenium is present, the catalyst may optionally contain rhenium as a co-promoter element, also in an amount of 5 to 2000 ppm.
According to another aspect of the present invention, there is also provided a process for the epoxidation of an olefin comprising: the silver catalyst is prepared by the method, and then olefin epoxidation reaction is carried out under the action of the silver catalyst.
According to the method disclosed by the invention, the silver catalyst is high in activity, good in stability and good in stability, so that the method is low in cost and high in reaction efficiency, and has extremely high economic and social benefits.
In one specific example, the olefin is ethylene and the epoxidation reaction yields ethylene oxide.
According to the invention, the carrier for the silver catalyst prepared by the preparation method has high crushing strength and large specific surface area, and the silver catalyst prepared by the carrier has high catalytic performance and good stability, meets the industrial application requirements for preparing the silver catalyst, has certain regulating capacity, and can improve the stability or other properties of the silver catalyst as required. The silver catalyst prepared by the method has the advantages of uniform silver particle distribution, less adhesion, high unit silver activity and contribution to improving the selectivity, the activity and the stability of the catalyst.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but do not limit the present invention.
(1) The crushing strength of the carrier is measured by adopting an intelligent particle strength tester;
(2) measuring the specific surface area of the carrier by using a NOVA2000e specific surface instrument;
(3) measuring the content of the substance attached to the carrier by X-ray fluorescence spectroscopy;
(4) the following instruments and methods were used to determine various indices of the catalyst:
the invention adopts a miniature tubular reactor (hereinafter referred to as 'micro-reactor') to evaluate the performance and stability of the initial catalytic reaction. The tubular reactor used in the method is a stainless steel reaction tube with the inner diameter of 4mm, and the reaction tube is arranged in a heating jacket made of copper or aluminum. After the silver catalyst particles are crushed, 0.8g of catalyst particles with the size of 12-18 meshes are screened and filled into a reactor to be compacted, and an inert filler is arranged at the lower part of the reactor to ensure that a catalyst bed layer is positioned in a constant temperature area of a heating sleeve.
The standard evaluation conditions for catalytic activity and selectivity adopted by the invention are as follows:
gas composition at the inlet of the reaction where the catalytic reaction is carried out (mol%): ethylene, 29.0 ± 1.0; oxygen, 7.3 +/-0.2; carbon dioxide, < 3.0; nitrogen, the balance; dichloroethane, 0.1-2.0 ppm. The reaction pressure is 2.1 MPa; the space velocity is 6000 h-1; the concentration of ethylene oxide in the reactor outlet tail gas was 2.5%.
The reactor was heated gradually from room temperature and, after the reaction had stabilized at operating conditions, the reactor inlet and outlet gas compositions were continuously measured. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas and Δ CO2 is the difference in carbon dioxide concentration between the reactor outlet gas and the inlet gas.
Example 1
Preparation of the support
359g of alumina trihydrate with 50 meshes, 120g of pseudo-alumina monohydrate with 200 meshes and 11g of ammonium fluoride are put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, 50g of petroleum coke and 190ml of dilute nitric acid with 20 wt% are added, and then the mixture is fully kneaded into pasty solid capable of being extruded and molded. Extruding and molding into a column with the outer diameter of 8mm, the length of 8mm and seven holes (the sizes of seven parallel holes are respectively 1.7mm of a central hole and 1.5mm of a peripheral hole), drying at 90-100 ℃ for more than 24 hours, then putting the molded carrier into a kiln, raising the temperature from room temperature to 1300 ℃ after 40 hours, and calcining at 1300 ℃ for 6 hours to obtain a white alumina carrier precursor.
A certain amount of solution is prepared for later use, wherein the concentration of ammonium metatungstate is 0.05 wt%, the concentration of manganese acetate is 0.10 wt%, and the concentration of ammonium rhenate is 0.10 wt%. 311g of the carrier precursor was weighed, completely immersed in the prepared solution, immersed under reduced pressure for 20 minutes, and filtered to remove the excess solution. And heating the impregnated carrier for 3min at 700 ℃ in an air atmosphere, and cooling to obtain a brown carrier product.
Preparation of the catalyst
49.1g of ethylenediamine and 12.7g of ethanolamine are dissolved in 100g of deionized water, 105.3g of silver oxalate is slowly added into the mixed solution under stirring, the temperature is kept below 40 ℃ to completely dissolve the silver oxalate, 0.24g of cesium nitrate and 0.11g of perrhenic amine are added, and the mixture is uniformly mixed to prepare impregnation liquid for later use.
Taking 30g of a carrier sample, putting the carrier sample into a container capable of being vacuumized, vacuumizing to reduce the pressure to be below 10mmHg, adding the impregnation liquid until the liquid surface is completely immersed in the solid, keeping for 30 minutes, and leaching to remove the redundant solution. The impregnated carrier is heated in air flow at 260 ℃ for 3 minutes and cooled to obtain the silver catalyst.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the results of semi-quantitative analysis of the content of the auxiliary on the carriers are shown in table 2, and the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Example 2
The support was prepared as in example 1, except that the heat treatment temperature was 300 ℃ and the catalyst was prepared as in example 1.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the results of semi-quantitative analysis of the content of the auxiliary on the carriers are shown in table 2, and the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Example 3
The support was prepared as in example 1 except that the solution formulation was changed to 0.10 wt% ammonium metatungstate and no manganese acetate or ammonium rhenate was added. The catalyst was prepared as in example 1.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the results of semi-quantitative analysis of the content of the auxiliary on the carriers are shown in table 2, and the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Example 4
The support was prepared as in example 1 except that the solution formulation was changed to 0.10 wt% manganese acetate and no ammonium metatungstate and ammonium rhenate were added. The catalyst was prepared as in example 1.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the results of semi-quantitative analysis of the content of the auxiliary on the carriers are shown in table 2, and the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Example 5
The support was prepared as in example 1 except that the solution formulation was changed to 0.10 wt% ammonium rhenate without the addition of manganese acetate and ammonium metatungstate. The catalyst was prepared as in example 1.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the results of semi-quantitative analysis of the content of the auxiliary on the carriers are shown in table 2, and the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Comparative example 1
The support was prepared as in example 1, except that the support precursor was not treated with the impregnation liquid. The catalyst was prepared as in example 1.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the content of the semi-quantitative analysis result of the auxiliary on the carriers is shown in table 2, the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Comparative example 2
The support was prepared as in example 1, except that the support precursor was not treated with the impregnation liquid. The preparation process of the catalyst is based on the example 1, and the following substances are added into the impregnation liquid: ammonium metatungstate concentration 0.05 wt%, manganese acetate concentration 0.10 wt%, and ammonium rhenate concentration 0.10 wt%, based on the impregnation solution.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the content of the semi-quantitative analysis result of the auxiliary on the carriers is shown in table 2, the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
Comparative example 3
The support was prepared as in comparative example 2. Preparation of catalyst ammonium metatungstate was added to the impregnation solution based on example 1, at a concentration of 0.10 wt%.
The carriers were tested, and the test results are shown in table 1, and since the content of each auxiliary was extremely low, accurate detection was difficult, the content of the semi-quantitative analysis result of the auxiliary on the carriers is shown in table 2, the obtained silver catalysts were evaluated for one month using a microreactor evaluation apparatus according to the aforementioned evaluation method, and the experimental results are shown in table 3.
As seen in table 1, compared to comparative example 1, the carrier prepared by the preparation method described in the present invention has high crushing strength and large specific surface area.
As can be seen from the data in table 3, comparing the data in example 1 with those in comparative examples 1 and 2, the supported silver catalyst prepared by the preparation method of the present invention has good catalytic performance, especially, the reaction temperature is substantially maintained, the stability is greatly improved, and the selectivity is improved. Comparing example 3 with comparative example 3, the method of the present invention greatly reduces the reaction temperature, improves the catalyst activity, and also improves the selectivity and stability.
TABLE 1
| Crush strength (N/grain) | Specific surface area (m)2/g) | |
| Example 1 | 92 | 1.66 |
| Example 2 | 85 | 1.79 |
| Example 3 | 60 | 1.73 |
| Example 4 | 76 | 1.72 |
| Example 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%) | |
| Example 1 | 0.03 | 0.05 | 0.03 |
| Example 2 | 0.03 | 0.05 | 0.05 |
| Example 3 | 0.05 | 0.00 | 0.005 |
| Example 4 | 0.00 | 0.05 | 0.00 |
| Example 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
It can be known from the comparison of data that the method provided by the invention has the advantages of uniform silver particle distribution, less adhesion, no sacrifice of active sites on the surfaces of silver particles in the catalyst while exerting the effects of tungsten and/or manganese and/or rhenium, and improvement of selectivity, activity and stability of the silver catalyst.
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. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (19)
1. A method for preparing a carrier for a silver catalyst, comprising the steps of:
I. preparing a mixture comprising alumina trihydrate, pseudo-alumina monohydrate, a fluoride mineralizer, and a burnout lubricant;
II, kneading the mixture with a binder, drying, and then roasting to obtain a precursor of the alumina carrier;
and III, dipping a precursor of the carrier in a solution, wherein the solution contains at least one compound selected from a tungsten compound, a manganese compound and a rhenium compound, then carrying out solid-liquid separation, and then carrying out heat treatment on the solid phase, wherein the temperature of the heat treatment is 150-750 ℃, so as to obtain the carrier for the silver catalyst.
2. The method as claimed in claim 1, wherein, in the step III, the temperature of the heat treatment is 300-700 ℃; and/or the time of the heat treatment is 1 to 600 minutes.
3. The method according to claim 2, wherein in the step III, the time of the heat treatment is 1 to 30 minutes.
4. The method according to any one of claims 1 to 3, wherein in the step III, the concentration of the tungsten compound in the solution is 2 wt% or less; and/or the concentration of the manganese compound is less than 2 wt%; and/or the concentration of the rhenium compound is 2 wt% or less.
5. The method according to claim 4, wherein in the step III, the concentration of the tungsten compound in the solution is 0.01-2 wt%; and/or the concentration of the manganese compound is 0.01-2 wt%; and/or the concentration of the rhenium compound is 0.01 to 2 wt%.
6. The method according to claim 4, wherein in the step III, the concentration of the tungsten compound in the solution is 0.01 to 1 wt%; and/or the concentration of the manganese compound is 0.01 to 1 wt%.
7. A method according to any one of claims 1 to 3, wherein the tungsten compound is selected from at least one of ammonium metatungstate, sodium tungstate and potassium tungstate; and/or the manganese compound is selected from at least one of potassium permanganate, potassium acetate and potassium sulfate; and/or the rhenium compound is selected from at least one of potassium perrhenate, ammonium perrhenate and perrhenic acid.
8. The method according to any one of claims 1 to 3, wherein the mass ratio of alumina trihydrate to pseudo-alumina monohydrate is (0.5 to 4):1, and/or
The alumina trihydrate is selected from at least one of α -alumina trihydrate and β -alumina trihydrate, and/or the fluoride is selected from at least one of ammonium fluoride, aluminum fluoride and potassium fluoride, and/or the burnout lubricating material is selected from at least one of petroleum coke, graphite and vaseline.
9. The method according to any one of claims 1 to 3, wherein the binder is an acid solution; and/or the acid to water mixing precursor volume ratio is between 1:10 and 1: 1; and/or the binder is used in an amount of 10 to 80 wt% based on the total weight of the mixture.
10. The method according to claim 9, wherein the binder is at least one selected from the group consisting of nitric acid, acetic acid, and an aqueous solution of citric acid.
11. A method according to any one of claims 1 to 3, wherein the drying temperature is 40 to 110 ℃ and the drying time is 24 to 72 hours; and/or the roasting temperature is 1200-1500 ℃, and the roasting time is 2-30 hours.
12. The method according to any one of claims 1 to 3, wherein the carrier for silver catalyst has a crushing strength of 30 to 200N/pellet and a specific surface area of 0.3 to 3m2/g。
13. The method according to claim 12, wherein the carrier for silver catalyst has a crush strength of 60 to 160N/pellet and a specific surface area of 1.6 to 2.5m2/g。
14. The method according to any one of claims 1 to 3, characterized in that the content by mass of the tungsten element is 2000ppm or less based on the total mass of the carrier; and/or the mass content of manganese element is below 2000 ppm; and/or the rhenium element mass content is 2000ppm or less.
15. A carrier for silver catalyst having an oxide of at least one selected from the group consisting of manganese oxide, tungsten oxide, and rhenium oxide attached to the surface thereof, which is produced by the production method according to any one of claims 1 to 14.
16. A method of preparing a silver catalyst comprising:
(1) the silver catalyst carrier according to claim 15, or the carrier for a silver catalyst prepared by the method according to any one of claims 1 to 14;
(2) and (2) soaking the carrier obtained in the step (1) in a soaking solution containing a silver-containing compound and organic amine, then carrying out solid-liquid separation, and activating a solid phase to obtain the silver catalyst.
17. The method according to claim 16, wherein in the step (2), the impregnation solution comprises an alkali metal assistant and/or an alkaline earth metal assistant and/or a rhenium assistant; when the impregnation liquid contains the rhenium auxiliary agent, a co-auxiliary agent of the rhenium auxiliary agent can be optionally contained.
18. A process for the epoxidation of an olefin comprising: use of the method according to claim 16 or 17 for the preparation of a silver catalyst, followed by epoxidation of an olefin under the action of the silver catalyst to obtain ethylene oxide after epoxidation.
19. The process of claim 18, wherein the olefin is ethylene.
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