CN107398303A - Catalyst carrier for producing ethylene oxide and preparation method and application thereof - Google Patents
Catalyst carrier for producing ethylene oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN107398303A CN107398303A CN201610333587.7A CN201610333587A CN107398303A CN 107398303 A CN107398303 A CN 107398303A CN 201610333587 A CN201610333587 A CN 201610333587A CN 107398303 A CN107398303 A CN 107398303A
- Authority
- CN
- China
- Prior art keywords
- carrier
- preparation
- catalyst
- acid
- attapulgite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 229960000892 attapulgite Drugs 0.000 claims abstract description 21
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 23
- 239000011707 mineral Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000002803 maceration Methods 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000007792 addition Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 8
- 241000219782 Sesbania Species 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 235000009496 Juglans regia Nutrition 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydroxypropyl Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 235000020234 walnut Nutrition 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 3
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VKPHHYUEMRNFSX-UHFFFAOYSA-N 2-aminobutan-2-ol Chemical compound CCC(C)(N)O VKPHHYUEMRNFSX-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- 238000001994 activation Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- 240000007049 Juglans regia Species 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 claims 1
- 230000001404 mediated effect Effects 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001935 peptisation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000758789 Juglans Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- 108091006146 Channels Proteins 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- B01J21/14—Silica and magnesia
-
- 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
- B01J21/12—Silica and 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst carrier for producing ethylene oxide, a preparation method of the carrier, a catalyst prepared by applying the carrier, and application of the catalyst in producing ethylene oxide by oxidizing ethylene. The invention relates to a carrier which is composed of an inner alumina matrix and an outer modified material surface. The carrier is obtained by adopting the method of stirring, soaking and roasting the transition phase-containing alumina carrier precursor in the attapulgite-containing slurry. The carrier prepared by the invention has the most probable pore diameter of 1000-1600 nm, the proportion of pores with the diameter less than 50nm in the total pores is less than 5%, and the pore volume is 0.3-0.6 ml/g. The modified material on the outer surface of the carrier is effective to disperse the silver active sites and prevent sintering thereof. The catalyst prepared by the carrier can show high selectivity and longer service life when used for preparing ethylene oxide by ethylene epoxidation.
Description
Technical field
The present invention relates to a kind of catalyst carrier for ethylene epoxidizing production reacting ethylene oxide and preparation method thereof
With the catalyst and preparation method thereof for being used to produce oxirane as made from the carrier.
Background technology
Ethylene epoxidizing is the production most important technique of oxirane, and its technological core is the silver catalyst of support type.Make
For loaded catalyst, the importance of technological improvement is exactly the improvement of carrier property, had at present substantial amounts of document and specially
Profit reports the effort of scientific research personnel in this respect.It can be found by the analysis to document, the improvement for carrier is mainly concentrated
Both direction is modified in the tuning of pore structure and surface.
Oxirane is simplest cyclic ethers, and its structure is very easy to open loop and other substance reactions, so chemical property
It is very active.The oxirane generated in the reaction of ethylene epoxidizing needs out of catalyst body phase to expand with faster diffusion rate
It is scattered in catalyst Outside Vapor, is otherwise easy to peroxidating.This just needs the duct of catalyst carrier to be advantageous to epoxy
The quick diffusion of ethane, the macropore ratio for improving carrier are effectively means, and roasting temperature is specifically improved in carrier preparation
Spend to realize.Particularly when sintering temperature is more than 1200 DEG C, not only obtain bigger pore-size distribution but also be also obtained
Be advantageous to the inert α-Al of oxirane generation2O3Surface.Although the corresponding bigger pore-size distribution of higher sintering temperature,
It also result in the low than surface and low pore volume of carrier simultaneously so that the water absorption rate of carrier declines, and dipping prepares the difficulty of catalyst
Degree increase.This, which is primarily due to high temperature, also there is the macropore in suitable aperture to burn other during aperture and mesoporous elimination
Lose.Patent CN103372466A, CN102397795A, CN102133545A are using variety classes and the diaspore knot of granular size
Conjunction mineralizer has obtained aperture and has accounted for 60-90% carrier in 0.5~2.5 μm of hole.Patent CN1361105A, CN1142154C is led to
Cross and add the tin compound of 0.01-0.48% weight and obtain diameter and account for the percentage of total pore volume more than 60 μm of hole being up to 20-
40% carrier.Although these methods can obtain the carrier that pore size is more biased towards big pore size distribution, but still contain and be largely unfavorable for
The aperture of Reaction-diffusion terms and mesoporous, and these patents are absorbed in the activity and selectivity for improving catalyst more, to catalyst
Life-span has no effective improvement.
Ethylene epoxidizing catalytic reaction occurs on the Argent grain of carrier surface load, so size of the reaction to Argent grain
Required with distribution.Argent grain is undersized, and catalyst activity is too high, will selectively reduce；It is oversized, activity will under
Drop is serious, and in particular with the use of catalyst, silver atoms can be moved on the surface of carrier, can finally be gathered into relatively large
Argent grain, cause the inactivation of catalyst.This explanation wants to reach suitable activity and high selectivity, and silver-colored dispersiveness has one
The scope of tuning, silver is hindered to extend the life-span of catalyst in the mobile can of carrier surface.Patent CN104981430A passes through
The surface of alumina support is modified, some cavitys are formed on surface, the cavity on these carrier surfaces effectively capture and/or
Grappling Argent grain and prevent them from further moving.A kind of carrying is disclosed in CN1080211A, 1050778C, 1044416A
The superficies and hole surface of body are applied coated with the side for reaching carrier surface modification with unbodied silica-alumina mixture
Method, wherein the effect of Si contents in coating is also specifically described, its Si/Al ratio is 0.05-50.0g/g, and this carrier has height
Durability, it is ensured that industrial longer service life.In addition patent CN1223900A, 1117618C,
102029154A, 101360562A also disclose that when the non-oxide aluminium component in surface such as Si compound in some preferred section it is right
The performance of carrier has positive-effect influence.It is steady that these patents have had been found that other oxide components of oxidation aluminium surface are used catalyst
Qualitatively influence, and the method utilized is proposed also for property, but improvement effect is very limited.On the one hand main cause is only
Modification of the silica to surface is make use of, is on the other hand that have ignored the influence during surface modification to carrier pore structure.
The content of the invention
The invention provides a kind of method for preparing modified aluminum oxide carrier.Carrier prepared by this method is by inside
Internal oxidation aluminum substrate and outside material modified surface composition.The structure will be contained by using heretofore described
The alumina support precursor for crossing phase stirs in the slurry containing alumina magnesia silicate, soak after the method that is calcined and obtain.
Its average pore size of carrier produced by the present invention is not less than 1100nm, and the hole accounting less than 50nm is less than 20%.Carrier external table
The material modified of face can effectively disperse silver-colored activated centre and hinder its sintering.
The method comprises the steps of firstly, preparing a kind of internal oxidation aluminum substrate containing transitional face, its specific way is：The first step will be with
The boehmite that 100 parts of quality meter mediates 0.5~3h of stirring in equal with peptizing agent, extrusion aid and pore creating material in kneader
Even bulk.Wherein peptizing agent is mainly organic acid, including formic acid, acetic acid, propionic acid, ethanedioic acid, malonic acid, succinic acid, lemon
At least one of acid and inorganic acid, including at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, meta-aluminic acid, peptizing agent is existed
5%~35% aqueous solution is formulated as in deionized water.Its feed postition be mediate stir during equably dropwise or
Spray adds, and preferable condition is can not to be less than the 60% of kneading time the addition time, and peptizing agent is 5~20 parts by mass.
The effect of extrusion aid is to aid in carrier and is preferably molded, predominantly the sesbania powder of 200~500 mesh, and addition is by mass 0.5
~3 parts.Extrusion aid can be added in kneader simultaneously with boehmite, can also uniformly be sprinkled into kneading after peptizing agent is added
In machine.Pore creating material is lost by being burnt in gaseous form in the roasting process of carrier, so as to be formed in the carrier to external open
Duct, it is carbon dust, walnut shell powder, ammonium hydrogen carbonate, starch, graphene, polymethyl methacrylate and a variety of Methyl celluloses
Element such as at least one of carboxymethyl cellulose, hydroxyethylmethylcellulose, hydroxypropyl methyl cellulose.Present invention discover that pore-creating
Influence of the granular size of agent to carrier aperture is notable, there is obvious corresponding relation between the two, and the granular size of pore creating material exists
Between 200~1000 mesh, can with boehmite simultaneously add or after peptizing agent with extrusion aid simultaneously add or it is crowded helping
Agent adds before or after adding, and addition is 10~35 parts by mass.
Second step carries out forming processes to the dough after kneading, and moulding process can again be cut into slices or directly be pressed using extrusion
Sheetmolding.Shape can be Raschig ring, middle non-porous or multiple hole column.The external diameter of Raschig ring is Particle
Length is 5.5~8.5mm, median pore diameterThe external diameter of cylindrical particle isParticle length is 6
~8mm.
Processing is dried to the particle after shaping in 3rd step.Drying mode can be selected but be not limited to crawler belt drying, heat
Air purging, oven drying.No matter which kind of mode, drying temperature is 100~200 DEG C, wherein it is preferred that 110~150 DEG C, more preferably
Be 120~140 DEG C.Drying time is 6~12h.
Final step is calcined to dried blapharoplast.Roasting apparatus can be Muffle furnace, tunnel cave or bell jar
One kind in kiln.The atmosphere that carrier contacts in roasting can be air, inert atmosphere or the inertia for adding certain proportion oxygen
Atmosphere.Inert atmosphere can be nitrogen or argon gas or helium.The heating rate of roasting be 2~20 DEG C, preferably 3~15
DEG C, more preferably 3~8 DEG C.2~4h of holding is needed when temperature rises to 800~1000 DEG C, is then proceeded to according to heating speed before
Rate rises to 1050~1450 DEG C, keeps 1~3h, naturally cools to room temperature.Because gamma-alumina is less than 1400 DEG C more than 800 DEG C
Meeting gradually changes through the opposite α phases of θ, but is unlikely to be completely reformed into α phases again within a certain period of time, but can be in a kind of including non-
γ, θ phase and the existing state of stable α phases in stable transition.So finally the internal oxidation containing transitional face is just obtained
Aluminum substrate.
The present invention also needs to prepare a kind of mineral slurry containing attapulgite material modified as the outside of carrier.It is prepared
Method is：By attapulgite, aluminium hydroxide and deionized water according to mass ratio 1~20:5~35：1000 are mixed and stirred for, process
The middle temperature for keeping mixed liquor is between 40~60 DEG C.It is gradually added dispersant in whipping process, dispersant and attapulgite
Mass ratio is 1:2~40.Wherein dispersant be 2-amino-2-methyl-1-propanol, dimethyl -1- amino -1- ethanol, citric acid,
At least one of polynary acid copolymer or homopolymer.Stop stirring after continuing 1~3h of stirring at low speed, taken after standing 1~3h
The uniform suspension of layer, then by the mass ratio 1 with attapulgite:4~15 add thickener, and wherein thickener changes for hydrophobicity
Property alkali-soluble emulsion type or polyurethanes thickener.Persistently stirring 0.5~3h after addition thickener can obtain containing attapulgite
Mineral slurry.
Internal oxidation aluminum substrate containing transitional face and the mineral slurry containing attapulgite are together synthesized processing system by the present invention
The carrier that must be modified.Internal oxidation aluminum substrate is immersed in the mineral slurry containing attapulgite first, it is slowly stirred 0.5~
1h, ensure that mineral slurry can uniformly touch all internal oxidation aluminum substrates, during keep the temperature of slurries 40~
70 DEG C, stirring soaks 10~36h after terminating.Concave convex rod crystal can be uniform and stable in the presence of thickener be attached to α oxygen
Change on aluminum substrate, simultaneously because concave convex rod crystal is in club shaped structure, width range is close with the pore size that aperture is mesoporous, is soaking
Dispersant helps to be sufficiently separated between concave convex rod crystal during bubble, the crystal of separation be embedded into aperture and it is mesoporous in, block
It is unfavorable for the channel pathway of reacting ethylene oxide diffusion.Next by the carrier soaked from the mineral slurry containing attapulgite
Filter to isolate and dry.Drying mode can select crawler belt drying, warm air blowoff or oven drying.Baking oven can use day
Right gas heat supply, electrical heating, steam heating or infrared heating.In any way, 100~150 DEG C of drying temperature, wherein it is preferred that
110~150 DEG C, more preferably 120~140 DEG C.Finally dried carrier is calcined, it is excellent with 1~10 DEG C per minute
Select 2~5 DEG C of speed from room temperature to 1300~1450 DEG C and keep 6~12h.The catalyst prepared using above method is carried
Body most probable pore size is between 1000~1600nm, and the ratio in wherein hole Zhan Zong hole of the aperture less than 50nm is less than 5%, and pore volume is situated between
In 0.3~0.6ml/g.Carrier forms obvious inner base and outside material modified combining structure, its inner base 95w%
Above by α-Al2O3Form；Outside is material modified to meet following chemical general formula：
AlMgaSibOx
A, b, x represent each element atomic ratio respectively, and wherein a is that 0.1~0.9, b is that 0.2~1.5, x is by each oxide
The numerical value that oxygen determines.
The invention further relates to the ethylene production oxirane prepared on the basis of a kind of carrier prepared in above-mentioned method
Catalyst, its preparation method is：The carrier for taking a certain amount of preceding method to prepare first, 3h is dried at 120 DEG C, take out cooling
After test its water absorption rate, the amount of preparation of maceration extract is calculated by the quality and water absorption rate and silver load capacity of carrier.Next,
At least one of silver nitrate, silver carbonate, actol are dissolved in deionized water, then carried out with the aqueous solution containing oxalate
Reaction obtains silver oxalate precipitate.The aqueous solution containing oxalate is oxalic acid or oxalic acid aqueous ammonium.Silver oxalate precipitate is filtered and taken out,
Then suction filtration is washed repeatedly with deionized water to filtrate in neutrality.Silver oxalate after washing is dissolved in into organic amine such as ethylenediamine, second
In the aqueous solution of hydramine, 1,3- propane diamine or its mixture, then add alkali metal or and base earth metal promoter be made dipping
Liquid.Wherein alkali metal is at least one of Li, K, Cs and Rb, and addition is Ag constituent contents in maceration extract by mass
0.1~1%.Alkaline-earth metal is one or more mixtures in Ca, Sr, Ba, and addition is Ag members in maceration extract by mass
The 0.05~0.5% of cellulose content.Maceration extract places 0.5~1h and carries out stabilization, while the temperature of maceration extract is maintained at into 20~40
℃.Afterwards in normal pressure or vacuum condition volumetric or excessive impregnated carrier.Carrier after dipping carries out drying and processing, drying side
Method and condition and internal oxidation aluminum substrate and the synthesis condition phase of mineral slurry containing attapulgite of the foregoing description containing transitional face
Together, processing 2-30 minutes obtain catalyst in 150-500 DEG C of temperature in air atmosphere after drying.Obtained catalyst after activation
High selectivity and the longer cycle of operation can be shown for ethylene epoxidizing epoxy ethane.
Due to using above-mentioned technical proposal, the beneficial effects of the present invention are：
(1) embedded concave convex rod crystal is made fully to be combined with the aluminum oxide of transition state by roasting, by between concave convex rod crystal
Too high ratio surface sintering, eliminates transition state of alumina, is allowed to be completely reformed into stable α phases, while embedding in this process
Enter the carrier surface protrusion of the outside of the concave convex rod crystal of aluminum oxide and the aluminum oxide formation of surrounding in magnesium alumino-silicate, these
Protrusion on alpha-aluminium oxide flat crystal particle is a significant increase the roughness on its surface, effectively Argent grain can be hindered to exist
Movement and reunion on carrier surface, delay silver-colored active sintering, extend the service life of catalyst.
(2) for the material modified alpha-aluminium oxide carrier in no outside, it is used to prepare carrier prepared by the present invention
The selectivity of oxirane can improve 1~6%, and successive reaction 1000h decay of activity rate can averagely decline 0.7%, table
Reveal longer catalyst life.
Embodiment
[characterizing method]
A. specific surface area：
Surface area described in the present invention refers in particular to B.E.T surface areas, can pass through any feasible method and reliable instrument
Device measures, but it is here preferred that the instruments of ASAP 2020 and standard GB/T19587-2004 using Merck ＆ Co., Inc of the U.S.
In method determine.
B. pore structure：
Because most of hole is macropore in carrier, reliable result can just only be obtained using pressure mercury.Here pore structure
Sign includes pore-size distribution, pore volume and porosity.The equipment used in embodiment is U.S. Mike mercury injection apparatus AutoPore9500
Mercury injection apparatus, method of testing is with reference to GB/T 21650.1-2008.
[evaluating catalyst experimental method]
A. reaction unit：
Reaction unit is mainly by gas mixing holder, mass flowmenter, pressure sensor, reactor and counterbalance valve five
It is grouped into.Reaction raw materials according to reaction condition gas mixing holder allocate, then by mass flowmenter measure control after
Be passed through in reactor and reacted, reactor byStainless steel tube, insideThermal couple casing pipe and electricity plus
Hot device composition, reaction pressure pass through counterbalance valve and pressure sensor adjustment control.
B. reaction condition：
Air speed=5000h-1；Reaction pressure=1.60Mpa；
Reaction raw materials：Ethene=30mol% oxygen=8mol% CO2=3mol% N2For Balance Air, wherein containing about 4~
6ppm monochlorethane.
C. analysis method：
Reacting gas passes to gas-chromatography by online pipeline and analyzed after standby pressure valve.
D. computational methods：
The present invention is described further with reference to embodiment, but the scope of the present invention is not limited to these examples.
[embodiment]
(1) internal oxidation aluminum substrate
Matrix A
1000g boehmites are weighed with electronic balance, the carbon dust of 67.9g1000 mesh is poured into kneader and mixed.
8.6g citric acids and 2.8ml concentrated nitric acids are weighed, peptization agent solution is made into 30ml deionized waters, is uniformly sprayed in 36 minutes
On the material of kneader, the sesbania powder 30g of 200 mesh is then added, is taken out after persistently mediating 36 minutes.Material after kneading is added
Pelletizing forms external diameter after entering double screw banded extruder extrusionMesoporeLength 6.5mm Raschig ring shape
Grain.
Shaped granule is put into the hot-air for being heated to 140 DEG C is passed through in tube furnace, dry 6h.Dried particle is put into
In Muffle furnace, it is calcined in air atmosphere.900 DEG C are risen to 8 DEG C/min speed, constant temperature 2h, is then followed by with before
Identical heating rate lifts temperature to 1350 DEG C, stops heating after holding 2h and is allowed to naturally cool to room temperature, obtains internal oxidation aluminium
Matrix A.
Matrix B
Preparation method and step and internal oxidation aluminum substrate A are essentially identical, and difference is：Peptization agent solution be by
27.5g succinic acid, the 22.5ml concentrated sulfuric acids and 171ml deionized waters are formulated.Peptization agent solution will uniformly add in 43 minutes
Enter.Sesbania powder addition is 10g, and mesh number is 500 mesh.Pore creating material is the walnut powder of the mesh of 240.9g 400, and is to add peptization
Added simultaneously with extrusion aid after agent.Persistently mediate 1.5h.Shaped granule is external diameterMesoporeLength
8.0mm Raschig ring shape.Roasting heating rate is 5 DEG C/min.
Matrix C
Preparation method and step and internal oxidation aluminum substrate A are essentially identical, and difference is：Peptization agent solution is by 3.5g
Succinic acid, 5.0ml concentrated hydrochloric acids and 72ml deionized waters are formulated.Peptization agent solution will be uniformly added into 38 minutes.Help crowded
Agent sesbania powder addition is 5g, and mesh number is 300 mesh.Pore creating material is the starch of the mesh of 133.1g 1000.Pore creating material adds in peptizing agent
Kneader uniformly is sprinkled into, then adds extrusion aid.Persistently mediate 1.5h.External diameter is shaped to using tablet press machineLength
The non-porous cylindrical pellet in 6.0mm centre.Using being put into Muffle furnace in the nitrogen containing 10% oxygen after 190 DEG C of dry 12h of baking oven
Under gas atmosphere, 900 DEG C, constant temperature 2h are risen to 10 DEG C/min, is then followed by lifting temperature to 1250 DEG C with identical heating rate before,
Stopping heating being allowed to naturally cool to room temperature after keeping 2h, obtains internal oxidation aluminum substrate C.
Matrix D
Weigh up 1000g boehmites, the extrusion aid sesbania powder of the mesh of 15g 400,400 mesh 64.8g walnut shell powders and
92.4g carboxymethyl celluloses, which are poured into kneader, to be mixed.Weigh 15.5g citric acids and 11.9g meta-aluminic acids, with 64ml go from
Sub- water is made into peptization agent solution, is uniformly sprayed in 44 minutes on the material of kneader, is taken out after persistently mediating 2h.It will pinch
Materials result after conjunction is shaped to external diameterLength 7.5mm, centre have 3The cylindrical pellet in hole.
Shaped granule is put into 110 DEG C of hot-air is passed through in tube furnace, dry 12h.Dried particle is put into Muffle
In stove, it is calcined in a nitrogen atmosphere.800 DEG C are risen to 2 DEG C/min speed, constant temperature 3h, is then followed by with identical liter before
Warm speed lifts temperature to 1150 DEG C, stops heating after holding 3h and is allowed to naturally cool to room temperature, obtains internal oxidation aluminum substrate D.
(2) mineral slurries
The preparation steps of mineral slurries are substantially identical：By M1G attapulgites, M2G aluminium hydroxides and 1500ml deionizations
Water weigh after be well mixed, during keep mixed liquor in temperature t1℃.M is gradually added in mixed process3G dispersants.Continue low
Speed stirring T1After stop, the uniform suspension in upper strata is taken after standing, then adds M4G thickeners.Persistently stir T2It can be contained
The mineral slurry of attapulgite.
Different mineral slurries are made from adding species by different additions, specific performance is shown in Table 1：
(wherein #1 thickeners are the RM-8W polyurethane thickeners of Rhom and Hass of the U.S., and #2 thickeners are U.S. Luo Men
The TT-935 hydrophobically-modified alkalis swelling association thickener of Haars Co., Ltd.)
Table 1
(3) carrier
Alpha-aluminium oxide matrix containing transitional face and the mineral slurry containing attapulgite are together synthesized into the obtained modified load of processing
Body.Internal oxidation aluminum substrate is immersed in the mineral slurry containing attapulgite first, is slowly stirred, ensures that mineral slurry can
Uniformly touch all internal oxidation aluminum substrates, during keep the temperature of slurries stirring soaked after terminating in some temperature
Regular hour.Modified support is formed by dry and roasting afterwards.
Directly internal oxidation aluminum substrate is calcined again and is made as comparison vehicle.
Specific performance is listed in table 2.
(4) catalyst
500g carriers are taken, 3h is dried at 120 DEG C, test its water absorption rate after taking out cooling, quality and water suction by carrier
The amount of preparation of maceration extract is calculated in rate and the silver load capacity of needs.Next, by silver nitrate, silver carbonate, actol
At least one silver salt is dissolved in deionized water, and silver oxalate precipitate is obtained with the reactant aqueous solution containing oxalate.Water containing oxalate
Solution is oxalic acid or oxalic acid aqueous ammonium.Silver oxalate precipitate is filtered and taken out, then washs suction filtration repeatedly with deionized water to filter
Liquid is in neutrality.Silver oxalate after washing is dissolved in into the water-soluble of organic amine such as ethylenediamine, monoethanolamine, 1,3- propane diamine or its mixture
In liquid, then add alkali metal or and base earth metal promoter be made maceration extract.Wherein alkali metal be Li, K, Cs and Rb in extremely
Few one kind, addition are 0.1~1% of Ag constituent contents in maceration extract by mass.Alkaline-earth metal is one in Ca, Sr, Ba
Kind or a variety of mixtures, addition are 0.05~0.5% of Ag constituent contents in maceration extract by mass.Maceration extract places 0.5
~1h carries out stabilization, while the temperature of maceration extract is maintained at into 20~40 DEG C.Load is being impregnated under normal pressure or vacuum condition afterwards
Body.Carrier after dipping carries out drying and processing, furnace drying method and condition and internal oxidation aluminum substrate of the foregoing description containing transitional face
It is identical with the synthesis condition of the mineral slurry containing attapulgite, after drying successively in 150-500 DEG C of air stream and water content
Processing 2-30 minutes obtain catalyst in 1%-100% vapor-air stream.
The catalyst of preparation carries out contrast test with foregoing evaluating apparatus and process conditions.
Specific preparation condition and test result are shown in Table 3.
Claims (35)
1. a kind of catalyst carrier for being used to prepare oxirane, it is characterised in that the carrier is by internal oxidation aluminum substrate and outside
Material modified composition, described more than internal oxidation aluminum substrate 95w% is by α-Al2O3Form, below outside material modified satisfaction
Chemical general formula：
AlMgaSibOx
A, b, x represent the atomic ratio of each element respectively, and wherein a is that 0.1~0.9, b is that 0.2~1.5, x is by the oxygen of each oxide
The numerical value of decision.
2. catalyst carrier as claimed in claim 1, it is characterised in that a is 0.1~0.3.
3. catalyst carrier as claimed in claim 1, it is characterised in that b is 0.2~0.5.
4. catalyst carrier as claimed in claim 1, it is characterised in that the most probable pore size of the catalyst carrier 1000~
Between 1600nm.
5. catalyst carrier as claimed in claim 1, it is characterised in that the wherein ratio in hole Zhan Zong hole of the aperture less than 50nm
Less than 5%.
6. catalyst carrier as claimed in claim 1, it is characterised in that pore volume is between 0.3~0.6ml/g.
7. according to the preparation method of any one of claim 1~6 carrier, it is characterised in that comprise the following steps:A) prepare
Internal oxidation aluminum substrate containing transitional face；B) mineral slurries containing attapulgite are prepared；C) by the internal oxidation aluminium containing transitional face
Matrix is stirred in the mineral slurries containing attapulgite, soaked；D) by the internal oxidation aluminum substrate after immersion from containing attapulgite
Mineral slurries in separate, be then dried and calcination process.
8. preparation method as claimed in claim 7, wherein the step of preparing the internal oxidation aluminum substrate containing transitional face includes：
A) it is extremely in uniform bulk boehmite and peptizing agent, extrusion aid and pore creating material to be mediated into stirring in kneader；
B) dough after mediating carries out forming processes；C) processing is dried in carrier；D) dried carrier is calcined.
9. preparation method as claimed in claim 8, it is characterised in that each component is respectively in mass in step a：100 parts of plans
Boehmite, 5~20 parts of peptizing agents, 0.5~3 part of extrusion aid, 10~35 parts of pore creating materials.
10. preparation method as claimed in claim 8, it is characterised in that the peptizing agent described in step a is organic acid formic acid, second
At least one of acid, propionic acid, ethanedioic acid, malonic acid, succinic acid, citric acid and inorganic acid hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,
At least one of meta-aluminic acid, described peptizing agent is formulated as to 5%~35% aqueous solution in deionized water.
11. preparation method as claimed in claim 8, it is characterised in that the peptizing agent described in step a is to mediate stirring
During equably dropwise or spray add.
12. preparation method as claimed in claim 8, it is characterised in that the extrusion aid described in step a is 200~500 purposes
Sesbania powder.
13. preparation method as claimed in claim 8, it is characterised in that the pore creating material described in step a is carbon dust, walnut shell
Powder, ammonium hydrogen carbonate, starch, graphene, polymethyl methacrylate, carboxymethyl cellulose, hydroxyethylmethylcellulose, hydroxypropyl
At least one of methylcellulose.
14. preparation method as claimed in claim 8, it is characterised in that pore creating material granular size described in step a 200~
Between 1000 mesh.
15. preparation method as claimed in claim 8, it is characterised in that the pore creating material described in step a can be with intending thin water aluminium
Stone adds or adds with extrusion aid after peptizing agent or added before or after extrusion aid addition simultaneously simultaneously.
16. preparation method as claimed in claim 8, it is characterised in that the forming processes described in step b can use extrusion again
Section or direct tablet compressing shaping.
17. preparation method as claimed in claim 8, it is characterised in that the shape described in step b after forming processes can be
Raschig ring, middle non-porous or multiple hole column.
18. preparation method as claimed in claim 17, it is characterised in that the external diameter of Raschig ring is 5.5-8.5mm, particle length
For 5.5~8.5mm, 1.5~5.5mm of median pore diameter, the external diameter of cylindrical particle is 6-8mm, and particle length is 6~8mm.
19. preparation method as claimed in claim 8, it is characterised in that drying mode can be selected but be not limited to carry out in step c
Drying, warm air blowoff and oven drying；100~200 DEG C of drying temperature, drying time are 6~12h.
20. preparation method as claimed in claim 8, it is characterised in that atmosphere when being calcined in step d can be air, inertia
Atmosphere or the mixed atmosphere containing air and inert gas.
21. preparation method as claimed in claim 8, it is characterised in that the heating rate being calcined in step d is 2~20 DEG C of heatings
To 800~1000 DEG C, 2~4h is kept, then rises to 1050~1450 DEG C according to heating rate before, keeps 1~3h.
22. the preparation method of the mineral slurries containing attapulgite, step include as recited in claim 7：A) by attapulgite,
Aluminium hydroxide is mixed and stirred for deionized water；B) dispersant and thickener are gradually added in whipping process；It is it is characterized in that recessed
The mass ratio of convex rod soil, aluminium hydroxide and deionized water is 1~20:5~35:1000.
23. the preparation method of the mineral slurries as described in claim 22, it is characterised in that described dispersant is 2- amino -2-
At least one of methyl isophthalic acid-propyl alcohol, dimethyl -1- amino -1- ethanol, citric acid, polynary acid copolymer or homopolymer, add
Amount and the mass ratio 1 of attapulgite:2~40.
24. the preparation method of the mineral slurries as described in claim 22, it is characterised in that lasting low speed stirs after adding dispersant
Mix and stop stirring after 1~3h, the uniform suspension in upper strata is taken after standing 1~3h, then add after thickener and persistently stir 0.5~
3h obtains the mineral slurry containing attapulgite.
25. the preparation method of the mineral slurries as described in claim 22, it is characterised in that described thickener changes for hydrophobicity
Property alkali-soluble emulsion type or polyurethanes thickener.
26. a kind of catalyst being used for by ethylene production oxirane, it is characterised in that the catalyst is by claim 1 to 6
Any carrier and argentiferous active component composition, the active component of described argentiferous is carried on described carrier.
27. a kind of method for preparing catalyst as claimed in claim 26, this method include：A) by the aqueous solution of silver salt compound
Reacted to obtain silver oxalate precipitate with the aqueous solution containing oxalate；B) silver oxalate after washing is dissolved in into Amine Solutions, and
Add alkali metal or and base earth metal promoter be made maceration extract；C) by any of claim 1 to 6 carrier impregnation in institute
In the maceration extract stated；D) catalyst is obtained after the activated processing of carrier after impregnating.
28. the method for preparing catalyst as described in claim 27, wherein the aqueous solution of described silver salt compound is by nitre
At least one of sour silver, silver carbonate, actol, which are dissolved in deionized water, to be formulated.
29. the method for preparing catalyst as described in claim 27, wherein the aqueous solution containing oxalate be oxalic acid or
Oxalic acid aqueous ammonium.
30. the method for preparing catalyst as described in claim 27, wherein described Amine Solutions are ethylenediamine, ethanol
The aqueous solution of amine, 1,3- propane diamine or its mixture.
31. the method for preparing catalyst as described in claim 27, wherein described alkali metal be in Li, K, Cs and Rb extremely
Few one kind, addition are 0.1~1w% of Ag constituent contents in maceration extract by mass.
32. the method for preparing catalyst as described in claim 27, wherein described alkaline-earth metal is one in Ca, Sr, Ba
Kind or a variety of mixtures, addition are 0.05~0.5w% of Ag constituent contents in maceration extract by mass.
33. the method for preparing catalyst as described in claim 27, wherein maceration extract need 0.5~1h of placement before impregnated carrier
Stabilization is carried out, while the temperature of maceration extract is maintained at 20~40 DEG C in dipping process.
34. the method for preparing catalyst as described in claim 27, it is characterised in that maceration extract is under normal pressure or vacuum condition
Isometric or excessive impregnated carrier.
35. the method for preparing catalyst as described in claim 27, it is characterised in that in air after the carrier drying after dipping
Activation process 2-30 minutes obtain catalyst in 150-500 DEG C of temperature under atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333587.7A CN107398303B (en) | 2016-05-19 | 2016-05-19 | Catalyst carrier for producing ethylene oxide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333587.7A CN107398303B (en) | 2016-05-19 | 2016-05-19 | Catalyst carrier for producing ethylene oxide and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107398303A true CN107398303A (en) | 2017-11-28 |
| CN107398303B CN107398303B (en) | 2018-08-07 |
Family
ID=60394057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610333587.7A Active CN107398303B (en) | 2016-05-19 | 2016-05-19 | Catalyst carrier for producing ethylene oxide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107398303B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608134A (en) * | 2020-12-10 | 2021-04-06 | 南昌大学 | Preparation method and application of porous ceramic ball catalyst |
| CN117398984A (en) * | 2022-07-04 | 2024-01-16 | 中国石油天然气股份有限公司 | Preparation method of α-alumina carrier, silver-loaded catalyst and preparation method thereof |
| CN119524826A (en) * | 2023-08-25 | 2025-02-28 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation and ethylene oxidation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100010234A1 (en) * | 2003-01-09 | 2010-01-14 | Ajinomoto Co. Inc | Process for manufacturing a glutamic acid derivative and a pyroglutamic acid derivative and a novel intermediate in the manufacture thereof |
| CN102247845A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Supported type silver catalyst and preparation method thereof |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method thereof, silver catalyst prepared from carrier and application of silver catalyst |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN104981430A (en) * | 2013-02-07 | 2015-10-14 | 科学设计公司 | Modified Supports for Silver-Based Ethylene Oxide Catalysts |
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
-
2016
- 2016-05-19 CN CN201610333587.7A patent/CN107398303B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100010234A1 (en) * | 2003-01-09 | 2010-01-14 | Ajinomoto Co. Inc | Process for manufacturing a glutamic acid derivative and a pyroglutamic acid derivative and a novel intermediate in the manufacture thereof |
| CN102247845A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Supported type silver catalyst and preparation method thereof |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method thereof, silver catalyst prepared from carrier and application of silver catalyst |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN104981430A (en) * | 2013-02-07 | 2015-10-14 | 科学设计公司 | Modified Supports for Silver-Based Ethylene Oxide Catalysts |
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608134A (en) * | 2020-12-10 | 2021-04-06 | 南昌大学 | Preparation method and application of porous ceramic ball catalyst |
| CN117398984A (en) * | 2022-07-04 | 2024-01-16 | 中国石油天然气股份有限公司 | Preparation method of α-alumina carrier, silver-loaded catalyst and preparation method thereof |
| CN119524826A (en) * | 2023-08-25 | 2025-02-28 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation and ethylene oxidation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107398303B (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100577289C (en) | Carrier of silver catalyst for ethylene oxide production, its preparation method and application | |
| CN106955744B (en) | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst | |
| CN102133545B (en) | Carrier, its preparation method and its application for ethylene oxide silver catalyst | |
| CN104549543B (en) | Alumina support, the silver catalyst being made from it and its application | |
| CN102746022B (en) | Preparation method of Al2O3 ceramic material with controllable bimodal porous structure | |
| CN103372466B (en) | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof | |
| CN105562113A (en) | Catalyst carrier and supported catalyst and their preparation methods and use and method for producing synthetic gas through dry reforming of methane | |
| CN107899619A (en) | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof | |
| CN107398303B (en) | Catalyst carrier for producing ethylene oxide and preparation method and application thereof | |
| CN108855238A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN103357441B (en) | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application | |
| CN104275212B (en) | Alpha-aluminium oxide carrier for silver catalyst and preparation method thereof | |
| CN107442109B (en) | Silver catalyst carrier, preparation method and application thereof | |
| CN106955692B (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application | |
| CN104549544B (en) | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application | |
| CN106955694B (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application | |
| CN104069893B (en) | Produce silver catalyst carrier, preparation method and application thereof for oxirane | |
| JP4726349B2 (en) | Catalyst for producing ethylene oxide, method for producing the same, and method for producing ethylene oxide using the catalyst | |
| CN109201027B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN102527442B (en) | A method for preparing an alumina support and the support obtained therefrom | |
| CN108250017A (en) | A method for selective hydrogenation of carbon three fractions | |
| CN108607617B (en) | Method for preparing alumina carrier for silver catalyst and silver catalyst | |
| CN117181207B (en) | Alpha-alumina carrier, preparation method thereof, silver catalyst and application thereof | |
| CN112007625A (en) | Alpha-alumina carrier, preparation method thereof, silver catalyst and application | |
| CN106955745A (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 730070 nanpoping village, shajingyi Township, Anning District, Lanzhou City, Gansu Province Patentee after: Lanzhou jinrunhongcheng New Material Technology Co.,Ltd. Address before: 730070 shajingyi nanpoping development community, Anning District, Lanzhou City, Gansu Province Patentee before: LANZHOU JRHC CHEMICAL TECHNOLOGY CO.,LTD. |