CN108686712A - Modified alpha-alumina supports and preparation method thereof and silver catalyst and application - Google Patents
Modified alpha-alumina supports and preparation method thereof and silver catalyst and application Download PDFInfo
- Publication number
- CN108686712A CN108686712A CN201710218015.9A CN201710218015A CN108686712A CN 108686712 A CN108686712 A CN 108686712A CN 201710218015 A CN201710218015 A CN 201710218015A CN 108686712 A CN108686712 A CN 108686712A
- Authority
- CN
- China
- Prior art keywords
- alpha
- alumina supports
- alumina
- water
- aluminium oxide
- Prior art date
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- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004332 silver Substances 0.000 title claims abstract description 73
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000012986 modification Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910052702 rhenium Inorganic materials 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- -1 Sodium alkyl benzene Chemical class 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000036314 physical performance Effects 0.000 description 4
- 229940100890 silver compound Drugs 0.000 description 4
- 150000003379 silver compounds Chemical class 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
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- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 description 3
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- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- WJNDLRMDNMIUGC-UHFFFAOYSA-N ethene;silver Chemical compound [Ag].C=C WJNDLRMDNMIUGC-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UDFWUWKGBBKQAF-UHFFFAOYSA-N oxalic acid;silver Chemical compound [Ag].OC(=O)C(O)=O UDFWUWKGBBKQAF-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910001845 yogo sapphire 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to epoxidation reaction of olefines field, it includes being molded the mesoporous macroporous aluminium oxide of alpha-alumina supports and growth on it to provide a kind of modified alpha-alumina supports and preparation method thereof and silver catalyst and application, the modification alpha-alumina supports;The crushing strength of the modified alpha-alumina supports is 55-220N, specific surface area 1.30-2.5m2/ g, Kong Rongwei 0.40-0.80mL/g, water absorption rate are not less than 42%;The pore size of the mesoporous macroporous aluminium oxide is 2-200nm.Invention increases the ducts of carrier, and compared with carrier made from the prior art, the modified alpha-alumina supports can improve dispersibility of the catalyst activity component on carrier.The silver catalyst made of the modification alpha-alumina supports shows good activity and higher selectivity during ethylene produces ethylene oxide.
Description
Technical field
The present invention relates to epoxidation reaction of olefines fields, specifically, the present invention provides a kind of modified alpha-alumina supports,
The preparation method of the modification alpha-alumina supports, the modification alpha-alumina supports being prepared by this method, the present invention also provides
A kind of silver catalyst and the modified alpha-alumina supports or silver catalyst answering in ethylene produces ethylene oxide
With.
Background technology
Silver catalyst effect under, ethylene mainly generates ethylene oxide, at the same can generate by-product carbon dioxide and
Water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to process for ethylene oxide production
Reach reaction temperature required when certain reaction load, reaction temperature is lower, and the activity of catalyst is higher;Selectivity refers to reaction
Middle ethylene is converted to the ratio between the molal quantity of ethylene oxide and the overall reaction molal quantity of ethylene;Stability is then expressed as activity and selection
The fall off rate of property, fall off rate is smaller, and the stability of catalyst is better.Make during ethylene produces ethylene oxide
Economic benefit can be greatly improved with high activity, silver catalyst that is highly selective and having good stability, therefore manufactures high activity, height
Selectivity and the silver catalyst having good stability are the Main ways of silver catalyst research.The performance of silver catalyst is removed and catalyst
Composition and preparation method have outside the Pass, the performance of carrier and preparation method thereof also used with catalyst has important relationship.
The preparation method of silver catalyst mainly include porous carrier (such as aluminium oxide) preparation and apply active component and
The two processes on auxiliary agent to the carrier.What carrier was generally selected is the smaller Alpha-alumina of specific surface area.Aluminium oxide has ten
Several crystal forms common are α, γ, θ, η and δ etc., and in these crystalline phases, α phases are stable phases, directly affect the property of silver catalyst
Energy.
Carrier, which needs to provide certain surface, carrys out load active component, and makes the evenly dispersed face on it of active component, this
Certain requirement just is proposed to the pore structure of carrier.The hole of alumina support can be divided into three classes:(1) primary particle intercrystalline hole,
The mainly dewatering hole of alumina raw material crystal grain, substantially gap between the parallel plate face of 1-2nm sizes;(2) alumina raw material two
Hole between secondary particle changes with the effusion of moisture and crystalline phase in calcining and is changed, and is the hole of tens nanometer or more;And (3) make
The defective hole and macropore that hole agent and carrier generate when being molded.
Silver catalyst carrier should not only have higher intensity, also want that specific surface and pore structure appropriate can be provided.Pass through
Molded carrier is handled, the dispersion situation of catalytic active component silver to carrier surface modification, can be improved, change load
The acid-base property in body surface face, the suction of modulation metal silver surface electronics situation and reaction species, desorption situation, to improve silver-colored catalysis
The catalytic performance of agent.This respect has some research work report.
Japan Patent JP2002136868 reports a kind of preparation method of alumina support:Support material is molded first
It is good, it is fired into the support precursor that main component is aluminium oxide at 500-2000 DEG C, then uses concentration 0.1-15%'s
Hydrofluoric acid solution processing gained presoma, a few hours are roasted at 1000-2000 DEG C, carrier finished product is formed, is carried by gained later
Silver catalyst prepared by body is had excellent performance.
German patent DE 2933950 reports a kind of method purified to silver catalyst carrier, which thinks to answer
Using pure Alpha-alumina as carrier material, if without the aluminium oxide of this purity, it can be to commercially available common Alpha-alumina
It is purified:30min is boiled with the NaOH solution of a concentration of 1wt% of about equivalent, is then washed with deionized, until moistening
Alpha-alumina pH value be less than 8.The patent thinks that other methods can also be used to obtain the carrier, such as using about equivalent
The hydrofluoric acid solution of concentration 1wt% boil carrier 10min, be then washed with water, until pH value is not less than 5.It is said that this method institute
After the silver catalyst of alkali metal containing auxiliary agent is made in carrier, activity and service life (stability) significantly improve, however selectivity
Also only 81.7% or so, and complex disposal process.
United States Patent (USP) US4786743A also illustrate it is a kind of by surface through pKa≤3 acid handle and contain step-like structure
Carrier made of silver catalyst, the silver catalyst have preferable thermal stability, activity and selectivity, however highest select
Property is also only 80% or so.
Patent documents above for the processing method of alumina support is directly located on molding alpha-alumina supports surface
Reason, these methods are limited to the active castering action of silver catalyst, and to the improvement effect unobvious of selectivity.Therefore, at present
The problem is that there is still a need for research and develop a kind of method that can improve silver catalyst activity and selectivity to a greater degree.
Invention content
The purpose of the present invention is overcoming the drawbacks described above of the prior art, providing a kind of makes silver catalyst meet high activity
There are more highly selective modification alpha-alumina supports and preparation method thereof simultaneously, including the silver of the modification alpha-alumina supports is urged
The application of agent and the modified alpha-alumina supports or silver catalyst in ethylene produces ethylene oxide.
It was found by the inventors of the present invention that directly being handled on molding alpha-alumina supports surface merely, the work to silver catalyst
Property castering action it is limited, and the raising of selectivity is acted on little.In order to improve the performance of alpha-alumina supports, inventor is directed to
Alpha-alumina supports have done numerous studies, find by the way that in the grown mesoporous macroporous aluminium oxide in alpha-alumina supports surface, being based on should
Carrier can prepare the better silver catalyst of selectivity.The present invention is based on what above-mentioned discovery was made.
According to the first aspect of the invention, the present invention provides a kind of modified alpha-alumina supports, the modification Alpha-aluminas
Carrier includes being molded the mesoporous macroporous aluminium oxide of alpha-alumina supports and growth on it;The pressure of the modified alpha-alumina supports
Broken intensity is 55-220N, specific surface area 1.30-2.5m2/ g, Kong Rongwei 0.40-0.80mL/g, water absorption rate are not less than 42%;
The pore size of the mesoporous macroporous aluminium oxide is 2-200nm, preferably 30-100nm.
According to the second aspect of the invention, the present invention provides a kind of preparation method of modified alpha-alumina supports, the party
Method includes:Molding alpha-alumina supports are mixed with mesoporous macroporous aluminium oxide precursor mixture, reacted, dry, roasting makes
Growth has mesoporous macroporous aluminium oxide in the molding alpha-alumina supports, to which the modified alpha-alumina supports be made.
According to the third aspect of the invention we, the present invention provides the modified alpha-carrying aluminas being prepared by the above method
Body.
According to the fourth aspect of the invention, the present invention provides a kind of silver catalyst, which includes:
Component a, the modification alpha-alumina supports;
Component b, silver;
Component c, alkali metal and/or alkaline-earth metal;
Component d, rhenium and its optional coassist agent;
Optional component e:Organic amine.
According to the fifth aspect of the invention, the present invention provides above-mentioned modified alpha-alumina supports or above-mentioned silver catalyst to exist
Ethylene produces the application in ethylene oxide.
The present invention is and existing by the grown mesoporous macroporous aluminium oxide in alpha-alumina supports surface, increasing the duct of carrier
There is carrier made from technology to compare, modification alpha-alumina supports of the invention have higher specific surface area, it is possible thereby to improve
Dispersibility of the catalyst activity component on carrier.Silver catalyst is in ethylene oxy metaplasia made of the modification alpha-alumina supports
Good activity and higher selectivity are shown during production ethylene oxide.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of modified alpha-alumina supports, the modification Alpha-aluminas
Carrier includes being molded the mesoporous macroporous aluminium oxide of alpha-alumina supports and growth on it;The pressure of the modified alpha-alumina supports
Broken intensity is 55-220N, specific surface area 1.30-2.5m2/ g, Kong Rongwei 0.40-0.80mL/g, water absorption rate are not less than 42%.
Under preferable case, the crushing strength of the modified alpha-alumina supports is 90-140N, specific surface area 1.30-
2.0m2/ g, Kong Rongwei 0.50-0.55mL/g, water absorption rate are not less than 50%.
It is highly preferred that the specific surface area of the modified alpha-alumina supports is 1.30-1.5m2/g。
Carrier of the modified alpha-carrying alumina be especially suitable for epoxidation of ethylene silver catalyst.The molding
The macropore meso-porous alumina of alpha-alumina supports surface portion attachment can increase the specific surface of carrier, reduce the flowing of silver particles
Property, the anti-caking power of silver catalyst is improved, the selectivity of catalyst is improved, extends the service life of catalyst.
The mesoporous macroporous aluminium oxide has rule or irregular pore passage structure, pore size 2-200nm.It is preferred that being situated between
The pore size of hole macroporous aluminium oxide is 30-100nm, can further increase the activity and selectivity of silver catalyst in this way.
In the present invention, the type of the mesoporous macroporous aluminium oxide can be the conventional selection of this field, for example, acid oxygen
Change one or more of aluminium, alkali alumina and neutral alumina.It is preferred that the mesoporous macroporous aluminium oxide is alkali alumina
And/or neutral alumina.
According to the second aspect of the invention, the present invention provides a kind of preparation method of modified alpha-alumina supports, the party
Method includes:Molding alpha-alumina supports are mixed with mesoporous macroporous aluminium oxide precursor mixture, reacted, dry, roasting makes
Growth has mesoporous macroporous aluminium oxide in the molding alpha-alumina supports, to which the modified alpha-alumina supports be made.
In the present invention, the conventional method that the molding alpha-alumina supports can refer to this field is prepared.According to one kind
Preferred embodiment, the molding alpha-alumina supports are made by the following method:By alumina raw material, binder and appropriate
Water mixing, be optionally added into auxiliary agent, obtain the precursor mixture of alpha-alumina supports;Then, by the precursor mixture into
Row kneading, molding, dry and roasting.
The alumina raw material refers to the silicon source that Alpha-alumina can be completely reformed into after roasting, and is including but not limited to hydrated oxygen
Change aluminium and/or transition aluminas.In a preferred embodiment, the alumina raw material is three water Alpha-aluminas and vacation one
Water aluminium oxide.Normally, with the total weight of alumina raw material, the dosage of the three water Alpha-alumina is 50-90wt%, described
The dosage of a false water aluminium oxide is 10-50wt%.
In addition, the granularity of the alumina raw material is conventional selection, for example, the three water Alpha-alumina can be 50-500
Mesh, the false water aluminium oxide can be more than 200 mesh.
The binder can generate Aluminum sol with alumina raw material, and each component is bonded together, extrudable molding is become
Paste.For example, the binder can be mixed into Aluminum sol with a false water aluminium oxide, therefore, the false water aluminium oxide,
Binder and water can provide directly in the form of Aluminum sol.Described adhesive can be selected from acid, such as nitric acid, formic acid, acetic acid, propionic acid
At least one of with hydrochloric acid, preferably nitric acid.
The binder and water can be individually added into, and can also be added in the form of adhesive solution, with the precursor
The addition of the total weight of mixture, the adhesive solution can be 15-60wt%, preferably 15-45wt%, into one
Step is preferably 15-35wt%, more preferably 15-25wt%.In the adhesive solution, the weight of the binder and water
Than that can be 1 ︰ (1.25-10), the weight ratio of the preferably described binder and water be 1 ︰ (4-5).It is described in the case of being individually added into
The addition of binder and water also meets above range.
The addition of the auxiliary agent can improve the pore structure and mechanical strength of alpha-alumina supports.The auxiliary agent is preferably silicon
One or more in simple substance, silicon-containing compound and alkaline earth metal compound, the silicon-containing compound is, for example, SiO2.Relative to
The dosage of the alumina raw material of 100 parts by weight, the auxiliary agent can be 0-5 parts by weight.
In order to which alpha-alumina supports precursor mixture each component to be uniformly mixed, the present invention mixes alpha-alumina supports precursor
It closes object to be mediated, kneading can carry out in kneader, and kneading time can be 5-90min.Alpha-alumina supports precursor is mixed
After closing object kneading fully, definite shape (molding) is made in carrier, the molding can carry out in molding machine.Molding α-the oxygen
Change the shape that alumina supporter can be this field routine, including but not limited to annular, spherical, cylindricality or porous column shape, specifically for example
The cellular cylindrical particle in outer diameter is 7-9mm, honeycomb aperture is 1-3mm seven apertures in the human head, five holes or three holes, it is outer diameter 7-9mm, interior
Diameter is the single hole annular shape particle etc. of 3-6mm.
After precursor mixture molding, molding is dried, which can carry out at 80-130 DEG C, will contain in molding
Water rate control is 10% hereinafter, drying time determines according to this;The time of the usual drying can be 1-24h.
Molding alpha-alumina supports with proper characteristics in order to obtain, the present invention roast the molding after drying.Institute
It includes temperature programming and constant temperature calcining process to state roasting, and the temperature of the constant temperature calcining can be 1000-1600 DEG C, the preferably described perseverance
The temperature of temperature roasting is 1100-1500 DEG C;The time of constant temperature calcining can be 2-24h.
In a particular embodiment, the molding alpha-alumina supports are made by following methods:
The three water Alpha-alumina, a false water aluminium oxide and optional auxiliary agent are mixed, solid mixture are made by step A;
Adhesive solution is added into the solid mixture in step B, obtains alpha-alumina supports precursor mixture;
Step C by alpha-alumina supports precursor mixture kneading, molding, drying and roasts, molding alpha-oxidation is made
Alumina supporter.
In the present invention, the concept of the mesoporous macroporous aluminium oxide precursor mixture is well known in the art, and refers to preparing to be situated between
The mixture of the various raw materials of hole macroporous aluminium oxide.
In one embodiment, the mesoporous macroporous aluminium oxide precursor mixture includes template, silicon source and water.
The template can be surfactant, different from other water-soluble polymers of surfactant and small point organic
One or more of sub- compound.It is preferred that the template be selected from cetyl trimethylammonium bromide, neopelex,
P123, polyethylene glycol, polyacrylamide, oleic acid list glyceric acid fat, acrylamide, glucose, sucrose, dibenzoyl-L- winestones
Acid and at least one of ethylene glycol, the more preferable template be in P123, polyethylene glycol, polyacrylamide and sucrose at least
It is a kind of.
Source of aluminium refers to organic aluminium salt and/or inorganic aluminate, is preferably selected from aluminium isopropoxide, isobutanol aluminum, aluminum nitrate, sulphur
At least one of sour aluminium and sodium aluminate, more preferably aluminium isopropoxide and/or aluminum nitrate.
Normally, the weight ratio of the template, silicon source and water is 1 ︰ 0.5-10 ︰ 2-30.
In this embodiment, the molding alpha-alumina supports and mesoporous macroporous aluminium oxide precursor mixture are (with mould
The total amount meter of plate, silicon source and water) weight ratio be 1 ︰ 5-30, preferably 1 ︰ 5-25.
Under preferable case, the mesoporous macroporous aluminium oxide precursor mixture also includes pH adjusting agent and/or precipitating reagent.Institute
PH adjusting agent is stated for example selected from nitric acid, ammonium hydroxide, for the acid or mesoporous macroporous aluminium oxide of alkalinity, the precipitating reagent example to be made respectively
Such as it is selected from ammonium carbonate, urea.The pH adjusting agent, the dosage of precipitating reagent are known in the art, and details are not described herein.
According to a kind of specific implementation mode, the method for preparing modified Alpha-alumina includes the following steps:
1) template, silicon source and water are mixed, after silicon source dissolving, pH adjusting agent and optional precipitating reagent is added;
2) in hydrothermal reaction kettle (stainless steel cauldron of such as polytetrafluoroethyllining lining), by step 1) products therefrom and institute
Molding alpha-alumina supports mixing is stated, in 20-250 DEG C of (preferably 20-150 DEG C) hydro-thermal process 0.5-24h;
3) step 2) products therefrom is dried, roasted.It is preferred that being filtered to product before the drying, it is extra to remove
Liquid phase.
In addition, when the template is selected from polyacrylamide, the method for preparing modified Alpha-alumina includes the following steps:
1) source of aluminium, water, acrylamide and initiator are mixed, after silicon source dissolving, the molding alpha-oxidation is added
Alumina supporter and optional precipitating reagent;
2) after step 1) acquired solution is transparent, 60-120min is heated in 50-90 DEG C, causes acrylamide polymerization, obtains
Polyacrylamide wet gel;
3) the polyacrylamide wet gel is dry, roasting.
The initiator is the conventional selection of acrylamide polymerization reaction, such as selected from water-soluble peroxide, preferably
For ammonium persulfate;The weight ratio of the acrylamide monomer and initiator is usually 1 ︰ 0.01-0.5.
Molding alpha-alumina supports are mixed with mesoporous macroporous aluminium oxide precursor mixture, after reacted, the drying
It can be carried out at 50-130 DEG C, the dry time is usually in 10-50h;The roasting can carry out at 400-700 DEG C, when roasting
Between be 1-12h.
According to the third aspect of the invention we, the present invention provides the modified alpha-carrying aluminas being prepared by the above method
Body.Modified alpha-alumina supports obtained have the structure of modified alpha-alumina supports and physical property ginseng described in first aspect present invention
Number, details are not described herein.
According to the fourth aspect of the invention, the present invention provides a kind of silver catalyst, which includes:
Component a, above-mentioned modification alpha-alumina supports;
Component b, silver;
Component c, alkali metal and/or alkaline-earth metal;
Component d, rhenium and its optional coassist agent;
Optional component e:Organic amine.
In the silver catalyst, component c and d are the auxiliary agents of silver catalyst.Component b to d refers to being deposited in silver catalyst
Respective element.
The alkali metal is selected from least one of lithium, sodium, potassium, rubidium and caesium;The alkaline-earth metal be selected from calcium, magnesium, strontium and
At least one of barium.
In the present invention, the silver catalyst can be prepared in the usual way, such as by Ag-containing compound, organic amine, alkali metal
Auxiliary agent, base earth metal promoter, rhenium-containing auxiliary agent and its optional coassist agent apply (being coated or impregnated with) and arrive the modified Alpha-alumina
It is prepared on carrier.
The Ag-containing compound can be any Ag-containing compound suitable for preparing ethylene oxide silver catalyst, example
Such as one or more of silver oxalate, silver oxide and silver nitrate.
The organic amine can be any organic amine compound suitable for preparing ethylene oxide silver catalyst, as long as
The organic amine compound can form argent-amine complex with silver compound, such as selected from pyridine, butylamine, ethylenediamine, 1,3-
One or more of propane diamine, ethanol amine and triethylamine.It is preferred that the organic amine is ethylenediamine and/or ethanol amine.
The alkali metal promoter is selected from the compound of corresponding alkali metal (lithium, sodium, potassium, rubidium or caesium);Such as selected from the alkali
One or more of nitrate, sulfate and hydroxide of metal.
Preferably, the alkali metal promoter is one or more of lithium sulfate, cesium sulfate and cesium nitrate.
In the present invention, with silver catalyst total weight, the content of alkali metal element is logical in final obtained silver catalyst
It is often 0-2000ppm, preferably 5-1500ppm.
The base earth metal promoter is selected from the compound of corresponding alkaline-earth metal (magnesium, calcium, strontium or barium);Such as selected from the alkali
One or more of oxide, oxalates, sulfate, acetate and nitrate of earth metal.The base earth metal promoter is excellent
Compound of the choosing selected from barium and/or strontium, is more preferably selected from barium acetate and/or strontium acetate.
In the present invention, with silver catalyst total weight, the content of alkali earth metal in final obtained silver catalyst
Usually 0-2000ppm.
In the present invention, other than alkali metal above-mentioned, base earth metal promoter, in the preparation process of silver catalyst
The coassist agent of the rhenium auxiliary agent and optional rhenium that are added can be further improved the activity, selectivity and stabilization of silver catalyst
Property.
The rhenium-containing auxiliary agent can be selected from one or more of rhenium simple substance, the oxide of rhenium, perrhenic acid, perrhenate,
It is preferably selected from perrhenic acid and perrhenate, is more preferably selected from least one of perrhenic acid, perrhenic acid caesium and ammonium perrhenate.
In the present invention, with silver catalyst total weight, the content of rhenium element is usually in final obtained silver catalyst
5-1500ppm, preferably 10-1000ppm.
The coassist agent of rhenium can be any transition metal simple substance, boron or corresponding compound, institute in the periodic table of elements
It is, for example, chromium simple substance, molybdenum simple substance, tungsten simple substance, boron simple substance, chromium metallic compound, molybdenum compound, tungsten metallization to state coassist agent
It closes one or more in object and boron compound.
In the present invention, with silver catalyst total weight, the content of the coassist agent of rhenium is logical in final obtained silver catalyst
It is often 0-1000ppm.
In addition, the above auxiliary agent can be applied on the alumina support prior to, concurrently with, or after immersion silver, it can also
It is immersed on carrier after the silver compound is reduced.
According to a kind of embodiment, the silver catalyst is made by the following method:
1) with the solution of silver compound, organic amine, alkali metal promoter, rhenium-containing auxiliary agent and optional coassist agent containing sufficient amount
Impregnate above-mentioned modification alpha-alumina supports;
2) maceration extract, and dry impregnated carrier are filtered off;And
3) in containing oxygen gas mixture, to being activated through impregnated carrier, to which the silver catalyst be made.
In step 1), specifically can first it use silver-colored described in the aqueous dissolution of organic amine (such as ethylenediamine and/or ethanol amine)
Compound (such as silver oxalate) generates argent-amine complex, then is made into the maceration extract with auxiliary agents such as above-mentioned alkali metal;
In step 3), the purpose of activation is that product, which is carried out thermal decomposition, is made finished product silver catalyst.Wherein, the activation
It can be carried out in the nitrogen oxygen atmosphere of air stream or oxygen content no more than 21v% (such as oxygen-containing 8.0v%), the temperature of activation is logical
It it is often 180-700 DEG C, preferably 200-500 DEG C, the time of activation can be 20 seconds to 120 minutes, preferably 1-60 minutes.
According to a kind of more specific embodiment, the silver catalyst is prepared by the following method:
First, so that the aqueous solution of silver nitrate is reacted with ammonium oxalate or oxalic acid aqueous solution, silver oxalate precipitate is precipitated, after filtering,
Be washed with deionized, up to no nitrate ion, then silver oxalate dissolved in the aqueous solution of organic amine, add it is above-mentioned its
It is mixed to be made into dipping for its auxiliary agent (coassist agent of alkali metal promoter and/or base earth metal promoter, rhenium metal promoter and optional rhenium)
Close solution;
Then, above-mentioned modified alpha-alumina supports are impregnated with dipping mixed solution, are drained, in the air stream or nitrogen oxygen
It is activated in gaseous mixture, to be thermally decomposed.
In the specific embodiment, it is also possible to silver oxide replaces silver nitrate, and silver oxalate can not also analyse filter, directly with have
Machine amine is complexed, then impregnated carrier.
In the present invention, the amount of the silver compound used in dipping process makes with silver catalyst total weight, final made
The content of silver element is 1-30wt%, preferably 5-26wt% in the silver catalyst obtained.
According to the fifth aspect of the invention, the present invention provides above-mentioned modified alpha-alumina supports or the silver catalyst to exist
Ethylene produces the application in ethylene oxide.The silver catalyst of the present invention produces ethylene oxide especially suitable for ethylene
In technique, good activity and selectivity is shown.
Term " optionally " of the present invention refers to " optionally " containing or not contain, and also refers to be added or be added without.
" water " word of the present invention refers to deionized water, distilled water in the case of no particularly specified or explanation
One or more of with ultra-pure water.
Heretofore described term " coassist agent of rhenium " is also known as the collaboration auxiliary agent of " coassist agent of rhenium auxiliary agent " or rhenium.
The molecular formula of heretofore described term " aluminium oxide " is Al2O3。
To keep the present invention easier to understand, below in conjunction with embodiment, present invention be described in more detail, these implementations
Example only serve it is illustrative, be not intended to limit the present invention application range.
The detection method of the physical property of modified alpha-alumina supports is as follows in the present invention:
The specific surface area of carrier is measured according to international test standards ISO-9277 using nitrogen physisorption BET methods.Example
Such as, Kang Ta companies NOVA2000e type nitrogen physisorption instrument in the U.S. can be used to measure the specific surface area of carrier.
Term " water absorption rate " used refers to the volume of the carrier saturation absorption water of unit mass in the present invention, and unit is mL/
g.Its assay method is as follows:A certain amount of carrier is weighed first (it is assumed that its quality is m1), carrier is taken out after 1h is boiled in boiling water
It is erected on the moderate wet gauze of water content and removes the extra moisture of carrier surface, finally weigh the quality of the carrier after absorption water
(it is assumed that its quality is m2), the water absorption rate of carrier is calculated as follows.
Wherein, ρWaterIt is the density of the water under measuring temperature, atmospheric pressure.
The assessment method of silver catalyst performance is as follows in the present invention:
Various silver catalysts laboratory microreactor (hereinafter referred to as " micro- anti-") evaluating apparatus involved in the present invention
Test its initial activity and selectivity.The reactor used in micro anti-evaluation device is the stainless steel tube of internal diameter 4mm, and reaction tube is set
In heating mantle.The admission space of catalyst is 1mL, and there is inert filler in lower part, catalyst bed is made to be located at the constant temperature of heating mantle
Area.
The determination condition for the catalyst activity and selectivity that the present invention uses is as shown in table 1:
The determination condition of 1 catalyst activity and selectivity of table
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity S as follows after shrinking correction:
Wherein, Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2Reactor outlet gas with
Gas concentration lwevel is poor in inlet gas, takes test result of the average of 10 groups or more test datas as the same day.
Preparation example 1
This preparation example is molded alpha-alumina supports and preparation method thereof for illustrating.
By the α-three water A1 of 50-500 mesh2O3400g, the one water A1 of vacation more than 200 mesh2O3100g is put into blender and mixes
Close uniform, be transferred in kneader, the ︰ 5 of dust technology (Xiao Suan ︰ water=1, weight ratio is added) 90mL, it is kneaded into extrudable molding cream
Shape object.Extrusion molding is the five hole columns of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, is dried 2 hours at 80-120 DEG C
More than, so that free water content is reduced to 10% or less.Then it puts the green body into electric furnace, was increased to from room temperature through about 18 hours
1250 DEG C, constant temperature 4 hours obtains the molding α-A1 of white2O3Support samples are denoted as carrier D1, the related physical performance of the carrier
Data are shown in Table 2.
Embodiment 1-3 is used to illustrate the modification Alpha-alumina and preparation method thereof of the present invention.
Embodiment 1
At room temperature, 15g sucrose, 4.28g P123,15g aluminium isopropoxides and the mixing of 50g water are taken, tri- mouthfuls of burnings of 250mL are poured into
In bottle, start to stir, while it is 60 DEG C to control bath temperature, continues stirring until aluminium isopropoxide dissolves.It is added dropwise into solution
The salpeter solution of 10wt%, regulation system pH value are 5, and then stainless steel that obtained colloidal sol is poured into polytetrafluoroethyllining lining is anti-
It answers in kettle.The molding alpha-alumina supports prepared in 10g preparation examples 1 are taken to be put into reaction kettle, in room in the hydrothermal reaction kettle
Open reaction kettle is put into baking oven at 60 DEG C dry 48h by warm aging 10h after aging.Finally the solid of gained is placed in
Muffle furnace is warming up to 550 DEG C of roastings, and constant temperature 4h, and obtained product is made a living the Alpha-alumina with acid mesoporous macroporous aluminium oxide
Carrier (that is, described modified alpha-alumina supports), is denoted as support C 1, related physical performance data is shown in Table 2.
Embodiment 2
4.58g polyethylene glycol is dissolved in 70mL deionized waters, is stirred to clarify, the Al (NO of 14.3g are added3)3·
9H2O.Under intense agitation, above-mentioned solution is carried out cocurrent with the sal volatile of 0.5mol/L to mix, cocurrent adding material knot
Shu Hou, the pH value that mixed solution is adjusted using ammonia spirit are 9.This mixed solution is transferred to teflon lined not
In rust steel reaction kettle.The carrier D1 prepared in 10g preparation examples 1 is taken to be put into reaction kettle, it is anti-in 100 DEG C in the hydrothermal reaction kettle
Should for 24 hours, obtained solid in 80 DEG C of dry 48h, is put into Muffle furnace and is warming up to 550 DEG C of roastings, and constant temperature 4h, obtained by filtering
Product is made a living the alpha-alumina supports with the mesoporous macroporous aluminium oxide of alkalinity, is denoted as support C 2, related physical performance data is shown in
Table 2.
Embodiment 3
At room temperature, 8.0g aluminum nitrates is taken to be dissolved under stiring in 45mL distilled water, add 2.1g acrylamide and
0.8g ammonium persulfates.After stirring 30min, 2.8g urea is added.It takes the carrier D1 prepared in 10g preparation examples 1 to be put into wherein, waits for
After solution clear, it is placed in 60 DEG C of baking ovens and heats 90min, to cause the polymerization of acrylamide.End to be polymerized
Afterwards, gained wet gel is placed in 80 DEG C of baking ovens dry 48h.The polymer is placed in Muffle furnace and rises to 550 DEG C of roastings, and is permanent
Warm 4h, obtained product make a living the alpha-alumina supports with neutral mesoporous macroporous aluminium oxide (that is, the modified alpha-carrying alumina
Body), it is denoted as support C 3, related physical performance data is shown in Table 2.
The physical data of 2 carrier of table
* it notes:The pore-size distribution refers to the pore-size distribution model for being not added with the pure mesoporous macroporous aluminium oxide of 1 carrier of preparation example synthesis
It encloses.
It can be seen that by the data in contrast table 2 and grown the alpha-alumina supports of mesoporous macroporous aluminium oxide and increase
The duct of carrier improves the specific surface area of alpha-alumina supports.
Embodiment 4-6 and comparative example 1
700g silver nitrates are taken to be dissolved in 750mL deionized waters.325g ammonium oxalate is taken to be dissolved in the deionized water of 50 DEG C of 250mL
In.Two kinds of solution are mixed with vigorous stirring, generate white silver oxalate precipitate.Aging 30 minutes or more, filtering, uses deionized water
Washing is precipitated to no nitrate ion, obtains silver oxalate paste, the paste argentiferous about 60wt%, aqueous about 15wt%.
Add 300g ethylenediamines and 485g deionized waters in the glass flask with stirring.Stir lower oxalic acid silver paste obtained
Shape object is slowly added into mixed liquor, and temperature is maintained at 45 DEG C hereinafter, making silver oxalate all dissolvings, addition 4.2g cesium sulfates and 0.2g
Ammonium perrhenate, then add deionized water that solution gross mass is made to reach 2000g, dipping mixed liquor is made.The addition of silver oxalate makes leaching
Stain mixed liquor argentiferous 23-25wt%.
The support samples for taking 50g embodiments 1-3 and preparation example 1 respectively are put into the container that can be vacuumized.It is evacuated to true
For reciprocal of duty cycle in 10mmHg or more, every part of carrier is put into the dipping mixed liquor 100g of above-mentioned preparation, submerges carrier and keeps 30min.Drip
Filter off extra solution.Carrier after dipping heats 10min in 275 DEG C of air stream, cooling, that is, ethylene oxide silver is made and urges
Agent is denoted as the silver catalyst of embodiment 4-6 and comparative example 1 respectively.
The silver content of manufactured catalyst is analyzed, content is with elemental metal;It is evaluated and is filled using microreactor
The activity and selectivity that catalyst sample is measured under the conditions of previous process is set, test result is listed in table 3.
3 silver catalyst ethylene oxide of table produces the test result of ethylene oxide
* it notes:Selectivity takes accumulative EO yield to reach 400T/M3Average value when catalyst.
The mesoporous macroporous aluminium oxide in the alpha-alumina supports growth present invention is can be seen that by the data in contrast table 3
Afterwards, the selectivity of silver catalyst is promoted more apparent, especially compared with carrier does not make the catalyst of modification, is selectively carried
High 1.5-3%, says from this aspect, and silver catalyst performance gets a promotion highly significant.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (12)
1. a kind of modified alpha-alumina supports, which is characterized in that the modification alpha-alumina supports include molding alpha-alumina supports
With the mesoporous macroporous aluminium oxide of growth on it;The crushing strength of the modified alpha-alumina supports is 55-220N, specific surface area
For 1.30-2.5m2/ g, Kong Rongwei 0.40-0.80mL/g, water absorption rate are not less than 42%;The aperture of the mesoporous macroporous aluminium oxide
Size is 2-200nm, preferably 30-100nm.
2. a kind of preparation method of modified alpha-alumina supports, which is characterized in that this method includes:Alpha-alumina supports will be molded
It mixes, reacted, dry, roasting, makes raw in the molding alpha-alumina supports with mesoporous macroporous aluminium oxide precursor mixture
With mesoporous macroporous aluminium oxide, to which the modified alpha-alumina supports be made.
3. preparation method according to claim 2, wherein the mesoporous macroporous aluminium oxide precursor mixture includes mould
Plate, silicon source and water;It is preferred that the weight ratio of the template, silicon source and water is 1 ︰ 0.5-10 ︰ 2-30;
Preferably, the molding alpha-alumina supports and the weight ratio of mesoporous macroporous aluminium oxide precursor mixture are 1 ︰ 5-30.
4. preparation method according to claim 3, wherein the template is selected from cetyl trimethylammonium bromide, 12
Sodium alkyl benzene sulfonate, P123, polyethylene glycol, polyacrylamide, oleic acid list glyceric acid fat, acrylamide, glucose, sucrose, connection
Benzoyl-at least one of L-TARTARIC ACID and ethylene glycol;Source of aluminium is selected from aluminium isopropoxide, isobutanol aluminum, aluminum nitrate, sulfuric acid
At least one of aluminium and sodium aluminate.
5. preparation method according to claim 4, wherein the mesoporous macroporous aluminium oxide precursor mixture also includes pH
Conditioning agent and/or precipitating reagent.
6. preparation method according to claim 5, wherein the described method comprises the following steps:
1) template, silicon source and water are mixed, after silicon source dissolving, pH adjusting agent and optional precipitating reagent is added;
2) in hydrothermal reaction kettle, step 1) products therefrom is mixed with the molding alpha-alumina supports, in 20-250 DEG C of water
It is heat-treated 0.5-24h;
3) step 2) products therefrom is dried, roasted.
7. preparation method according to claim 5, wherein the described method comprises the following steps:
1) source of aluminium, water, acrylamide and initiator are mixed, after silicon source dissolving, the molding Alpha-alumina is added and carries
Body and optional precipitating reagent;
2) after step 1) acquired solution is transparent, 60-120min is heated in 50-90 DEG C, causes acrylamide polymerization, obtains poly- third
Acrylamide wet gel;
3) the polyacrylamide wet gel is dry, roasting.
8. preparation method according to claim 2, wherein the molding alpha-alumina supports are prepared by the following method
It arrives:Alumina raw material, binder and water are mixed, auxiliary agent is optionally added into, obtains alpha-alumina supports precursor mixture, then
The alpha-alumina supports precursor mixture is mediated, is molded, is dried and is roasted;The alumina raw material is preferably three water
Alpha-alumina and a false water aluminium oxide.
9. according to the preparation method described in any one of claim 2,6 and 7, wherein the temperature of the drying is 50-130
DEG C, drying time 10-50h;The temperature of the roasting is 400-700 DEG C, roasting time 1-12h.
10. the modification alpha-alumina supports that any one of claim 2-9 the methods are prepared.
11. a kind of silver catalyst, which is characterized in that the silver catalyst includes:
Component a, the modification alpha-alumina supports described in claim 1 or 10;
Component b, silver;
Component c, alkali metal and/or alkaline-earth metal;
Component d, rhenium and its optional coassist agent.
12. the silver catalyst described in modification alpha-alumina supports or claim 11 described in claim 1 or 10 is in ethylene
Application in epoxidation reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113649032A (en) * | 2021-08-18 | 2021-11-16 | 金华永和氟化工有限公司 | Vinylidene fluoride catalyst and preparation method thereof |
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