CN101376111A - 用于生产轻质烯烃的水处理催化剂 - Google Patents
用于生产轻质烯烃的水处理催化剂 Download PDFInfo
- Publication number
- CN101376111A CN101376111A CN 200810212523 CN200810212523A CN101376111A CN 101376111 A CN101376111 A CN 101376111A CN 200810212523 CN200810212523 CN 200810212523 CN 200810212523 A CN200810212523 A CN 200810212523A CN 101376111 A CN101376111 A CN 101376111A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ammonium
- molecular sieve
- water
- tetraethyl
- 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 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001868 water Inorganic materials 0.000 title claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 title claims description 17
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 3
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 3
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 238000009415 formwork Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 3
- QDVBKXJMLILLLB-UHFFFAOYSA-N 1,4'-bipiperidine Chemical class C1CCCCN1C1CCNCC1 QDVBKXJMLILLLB-UHFFFAOYSA-N 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 2
- RCZLVPFECJNLMZ-UHFFFAOYSA-N n,n,n',n'-tetraethylpropane-1,3-diamine Chemical class CCN(CC)CCCN(CC)CC RCZLVPFECJNLMZ-UHFFFAOYSA-N 0.000 claims description 2
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- AJPPAKACCOFNEN-UHFFFAOYSA-K tetraethylazanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC AJPPAKACCOFNEN-UHFFFAOYSA-K 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000004927 clay Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 229940037003 alum Drugs 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 235000019795 sodium metasilicate Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910003452 thorium oxide Inorganic materials 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 229910052649 zeolite group Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
给出了一种形成SAPO－34催化剂产物的方法。该方法，其包括用水或任选地至少溶解一种选自氯化铵、磷酸铵、醋酸铵、碳酸铵、硝酸铵和其混合物的固体的水处理，产生了用于乙烯和丙烯生产的增加的选择性的SAPO－34催化剂。
Description
发明领域
本发明涉及一种用于产生转化氧化物(oxygenate)成烯烃的催化剂的方法。该方法通过用水处理催化剂产生具有更好的产物选择性的催化剂。
发明背景
轻质烯烃是用于产生用在各种工业中的许多塑料产品的重要基础化学原料。烯烃一般通过较大烃分子的裂化从石油原料产生。裂化方法为催化或蒸汽裂化方法，并且生产主要由乙烯和丙烯构成的轻质烯烃。
轻质烯烃的替代来源来自氧化物到烯烃的转化。转化为烯烃的主要氧化物为甲醇。优选的方法一般指甲醇-至-烯烃(MTO)的方法。从这种方法产生的主要烯烃为乙烯和丙烯，并且该方法在催化分子筛上实施。MTO方法成为用于生产轻质烯烃的石油来源原料的主要替代品。氧化物来源包括醇，例如甲醇和乙醇；醚，例如二甲基醚和二乙基醚；和其它氧化物，例如甲酸甲酯和碳酸二甲酯。这些氧化物可以从天然气、生物物质发酵、市政废水和循环有机物质产生。重要的商业考虑是，甲醇可以很容易地从天然气、或煤生产，并且比天然气或煤更易于和更安全地处理和运输。
有很多专利描述了分子筛的改良的制备，US5,248,647描述了在超过700℃的温度下热处理硅铝磷酸盐分子筛充分的时间以破坏它们大部分的酸性位点，而保持它们至少80％的结晶度以形成用于转化甲醇成较低级的烯烃的催化剂。这种催化剂显示了提高的催化剂寿命、对C2和C3烯烃提高的选择性和相对于未处理的分子筛对链烷烃生产的降低的选择性。在US6,440,894中，卤素通过在400℃到1000℃温度下催化剂的蒸汽处理除去。分子筛或催化剂的类型、组成、大小和处理条件影响高收率的轻质烯烃的生产过程，并且需要大量的实验，在没有对特别的分子筛提供指导的情况下。
现有技术说明催化剂暴露于水导致催化剂的失活。例如，在US7,015,174中，有着对暴露于水引起的催化剂失活的很长的解释。与这个专利的教导相反，在本发明中已经发现用水处理导致催化剂具有对所希望的轻质烯烃提高的选择性。
特别希望提高希望的轻质烯烃——乙烯和丙烯的产率。因此，生产较高收率的这些希望的产物的催化剂会很有用。
发明概述
本发明提供了一种用水处理以提高对所希望的轻质烯烃生产的选择性的催化剂。该催化剂用在MTO方法中对催化剂具有物理损害的环境中。该催化剂包括分子筛，其从包括铝、磷、金属、水和有机模板的反应混合物中结晶出来。结晶后，洗涤分子筛，然后洗涤的分子筛与硅酸钠和酸明矾混合以形成催化剂料浆。催化剂料浆喷雾干燥以形成催化剂的硬颗粒。
本发明的另外的目标、实施方案和细节可以从本发明下面的详细描述中得到。
发明详述
SAPO-34分子筛属于具有沸石矿物菱沸石(CHA)结构类型的分子筛族。本领域已知SAPO-34的制备和特性，如在US4,440,871、US5,248,647和US6,953,767中例证的，其通过引用结合于此。
SAPO-34分子筛的制备包括提供包括铝、磷、水、有机模板和硅的反应混合物。这种制备更广泛地应用于ElAPO分子筛，其中元素El选自硅、镁、锌、铁、钴、镍、锰和铬中的一种或多种元素。得到的催化剂具有通过经验式表达的基于无水的化学组成：
(ElxAlyPz)O2。
“x”为El的摩尔分数并且值至少为0.001，“y”为Al的摩尔分数并且值至少为0.01，并且“z”为P的摩尔分数并且值至少为0.01。x、y和z的和等于1，或x+y+z＝1。
有机模板剂包括胺、和季铵化合物。模板剂的实例包括，但不限于吗啉、四乙基氢氧化铵(TEAOH)、四乙基磷酸铵、四乙基溴化铵、四乙基氯化铵、四乙基氟化铵、四乙基醋酸铵、二丙基胺(DPA)、异丙基胺、环己基胺、甲基丁基胺、二乙醇胺、吗啉、二乙基乙醇胺、N-甲基乙醇胺、四甲基氢氧化铵、仲-丁基胺、二甲基乙醇胺、N-甲基-丁基胺、甲基二乙醇胺、2，2-二甲基-1，3-丙烷二胺、环己基胺、三乙基胺、N，N，N’，N’-四甲基-亚乙基二胺、二异丙基胺、N-乙基-丁基胺、2-甲基-1，5-戊烷二胺、N，N-二甲基丁基胺、N，N，N’，N’-四甲基-1，3-丁烷二胺、N，N，N’，N’-四甲基-1，4-丁烷二胺、N，N-二甲基环己基胺、N，N-二甲基-苯甲基胺、C，C，C-三甲基-1，6-己烷二胺、N，N，N’，N’-四乙基-亚乙基二胺、4-哌啶基-哌啶、N，N，N’，N’-四乙基-1，3-丙烷-二胺、四丙基氢氧化铵、N，N，N’，N’-四乙基-二亚乙基三胺和1，1’-亚甲基-二(3-甲基哌啶)。
反应混合物在100℃到250℃的温度下结晶产生分子筛。然后洗涤得到的分子筛晶体。分子筛的正常处理包括分子筛的干燥。然而，这易于产生晶体的团聚。已经发现与形成后干燥晶体相反，更硬的、更耐磨的晶体可以通过新的方法形成。
洗涤分子筛后，形成了具有分子筛晶体的料浆而不干燥以维持小的晶体尺寸，向料浆中加入硅酸钠和酸明矾。料浆在高剪切混合器中混合并且喷雾干燥，产生小的硬得多并且更耐磨的催化剂产物颗粒。混合时间应该短以避免粘合剂凝胶化，并且应该在10秒到60分钟内。混合时间取决于在混合器和其它操作条件下的剪切的量。
作为替代，分子筛可以保持不洗涤，使用硅酸钠和酸明矾以及未洗涤的分子筛料浆。喷雾干燥允许残留的有机模板的蒸发。剩余的溶解的氧化物相信可以影响产物强度。
酸明矾是硫酸铝和硫酸的混合物。硅酸钠是氧化硅溶解在苛性(caustic)物质中的溶液，氧化硅和苛性物质的典型比为以重量计3:1。当酸明矾和硅酸钠混合时，得到的溶液为酸化水玻璃。两种溶液以产生具有2-3pH值的水玻璃的比例混合。
另外的粘合剂可以加入到料浆中，其包括但不限于氧化铝、氧化硅、氧化铝-氧化硅、磷酸铝、氧化钛和氧化锆。其它无机粘合剂也可用于这种方法中并且包括例如氧化镁、氧化铬、氧化硼、氧化钍和氧化锌。粘合剂也可作为胶体溶胶加入，其包括氧化硅、氧化铝、或氧化硅-氧化铝。应该注意术语氧化硅-氧化铝不是指氧化硅和氧化铝的物理混合物而是指共凝胶或共沉淀的酸性或无定形物质。在这些方面，可以形成其它共凝胶或共沉淀无定形物质，其作为粘合剂也是有效的。这些包括氧化硅-氧化镁、氧化硅-氧化锆、氧化硅-氧化钍、氧化硅-氧化铍、氧化硅-氧化钛、氧化硅-氧化铝-氧化钍、氧化硅-氧化铝-氧化锆、磷酸铝、其混合物等。
当形成催化剂产物时，分子筛具有15到50重量％的干燥催化剂产物的组成。在催化剂产物中的粘合剂形成10到90重量％的干燥催化剂产物。
优选任选地向催化剂中加入粘土。粘土一般在分子筛和粘合剂混合前加入催化剂料浆，得到的料浆混合并且喷雾干燥。当加入粘土时，粘土形成40到80重量％的干燥催化剂产物。在这些方法中使用以形成硬化产物的粘土包括，但不限于，高岭土、高岭石、蒙脱石、皂石、膨润土、绿坡缕石和叙永石。
粘土影响强度，而粘合剂提高催化剂颗粒的耐磨性质，并且粘土和粘合剂影响颗粒的硬度。粘土也以小颗粒开始并且具有较高的密度，以便当与分子筛和粘合剂结合时赋予更高密度的颗粒，使具有较高密度的希望性质。
耐磨催化剂对于在所需物理环境中的应用时是重要的，特别关注的是例如流化床等环境，其中催化剂连续翻腾并且与其它催化剂颗粒和反应器壁磨擦。因此，具有这种环境的MTO方法和耐磨SAPO-34催化剂是所希望的。
根据本发明，催化剂用水处理1到48小时的时间，优选6到36小时的时间并且最优选10到24小时的时间。水为在20℃到180℃的温度，优选20℃到100℃并且最优选25℃到60℃。在本文提供的实施例中，水为40℃。水处理后，催化剂在350℃干燥。任选地，水可以含至少一种溶解的固体，其选自氯化铵、磷酸铵、硫酸铵、醋酸铵、碳酸铵、硝酸铵和其混合物。
如下给出的实施例用于更充分地例证本发明的实施方案，并且不会限制如附带的权利要求给出的本发明的范围。
实施例
SAPO-34分子筛如在US5,126,308中的实施例2-5给出的生产，其通过引用结合于此。水处理研究包括3，5和12％三种不同SiO2水平SAPO-34粉末。粉末与9％的氧化硅使用胶体氧化硅(Ludox AS-40)连结，在650℃煅烧并且大小在250到2000微米范围。然后样品在催化剂：水重量比1：5时用水处理。样品在40℃处理48小时。处理后，在测试前样品在350℃干燥。
样品在MTO催化剂筛选装置测试。处理条件为435℃，35kPa(5psig)，在2.5的WHSV下80％的甲醇/水进料。在线GC附加在用于产物分析的装置上并且每20分钟收集数据。选择性数据在99.0％转化成甲醇和二甲基醚时记录。数据总结在如下表中并且显示了水处理后乙烯和丙烯组合选择性改善。另外，随着SAPO-34粉末中氧化硅水平提高选择性的改善提高了。
乙烯和丙烯选择性性能数据
尽管本发明已经用目前认为优选的实施方案说明，应当理解本发明不限于公开的实施方案，而是旨在覆盖附带的权利要求范围内包括的各种变更和等同方案。
Claims (10)
1.一种制备用于转化氧化物成烯烃的催化剂的方法，其包括:提供反应混合物，其包括铝、磷、水、有机模板和选自硅、镁、锌、铁、钴、镍、锰、铬和其混合物的元素，以形成具有如下经验式的基于无水的化学组成的非沸石分子筛:
(ElxAlyPz)O2
其中“x”为El的摩尔分数并且值至少为0.001，“y”为Al的摩尔分数并且值至少为0.01，并且“z”为P的摩尔分数并且值至少为0.01，x+y+z＝1；分子筛在100°到250℃结晶；
洗涤分子筛；
向洗涤分子筛加入粘合剂以形成催化剂料浆；
喷雾干燥催化剂料浆；
在高于500℃的温度煅烧以形成催化剂；并且
用水处理催化剂。
2.如权利要求1所述的方法，其中有机模板选自:四乙基氢氧化铵(TEAOH)、四乙基磷酸铵、四乙基溴化铵、四乙基氯化铵、四乙基氟化铵、四乙基醋酸铵、二丙基胺(DPA)、异丙基胺、环己基胺、甲基丁基胺、二乙醇胺、吗啉、二乙基乙醇胺、N-甲基乙醇胺、四甲基氢氧化铵、仲-丁基胺、二甲基乙醇胺、N-甲基-丁基胺、甲基二乙醇胺、2，2-二甲基-1，3-丙烷二胺、环己基胺、三乙基胺、N，N，N’，N’-四甲基-亚乙基二胺、二异丙基胺、N-乙基-丁基胺、2-甲基-1，5-戊烷二胺、N，N-二甲基丁基胺、N，N，N’，N’-四甲基-1，3-丁烷二胺、N，N，N’，N’-四甲基-1，4-丁烷二胺、N，N-二甲基环己基胺、N，N-二甲基-苯甲基胺、C，C，C-三甲基-1，6-己烷二胺、N，N，N’，N’-四乙基-亚乙基二胺、4-哌啶基-哌啶、N，N，N’，N’-四乙基-1，3-丙烷-二胺、四丙基氢氧化铵、N，N，N’，N’-四乙基-二亚乙基三胺和1，1’-亚甲基-二(3-甲基哌啶)和其混合物。
3.如权利要求1所述的方法，其中所述的催化剂具有SAPO-34组成和结构。
4.如权利要求1所述的方法，其中催化剂用水处理1-48小时的时间。
5.如权利要求1所述的方法，其中所述的催化剂用水处理6-36小时的时间。
6.如权利要求1所述的方法，其中所述的催化剂用水在20°到180℃的温度下处理。
7.如权利要求6所述的方法，其中所述的温度在20°到100℃。
8.如权利要求6所述的方法，其中所述的温度在25°到60℃。
9.如权利要求1所述的方法，其中所述的水进一步含至少一种溶解的固体，其选自氯化铵、磷酸铵、硫酸铵、醋酸铵、碳酸铵、硝酸铵和其混合物。
10.一种用于氧化物转化成烯烃的方法中的催化剂，其由权利要求1-9中任一项的方法制备。
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| US7241716B2 (en) * | 2003-11-10 | 2007-07-10 | Exxonmobil Chemical Patents Inc. | Protecting catalytic sites of metalloaluminophosphate molecular sieves |
| US20060224032A1 (en) * | 2005-03-29 | 2006-10-05 | Janssen Marcel J | Protecting catalytic sites of activated porous molecular sieves |
| US7550403B2 (en) * | 2005-06-30 | 2009-06-23 | Uop Llc | Methods for recovering activity of molecular sieve catalysts |
| US7309679B2 (en) * | 2005-08-08 | 2007-12-18 | Uop Llc | Attrition resistant MTO catalyst |
-
2007
- 2007-08-31 US US11/848,271 patent/US8815764B2/en active Active
-
2008
- 2008-08-29 RU RU2008135260/04A patent/RU2396116C2/ru not_active IP Right Cessation
- 2008-08-29 CN CN 200810212523 patent/CN101376111B/zh not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047802A1 (zh) * | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | 一种sapo-34分子筛及其合成方法 |
| WO2014047804A1 (zh) * | 2012-09-26 | 2014-04-03 | 中国科学院大连化学物理研究所 | 一种快速合成sapo-34分子筛的方法及由其制备的催化剂 |
| AU2012391395B2 (en) * | 2012-09-26 | 2016-10-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | SAPO-34 molecular sieves and synthesis method thereof |
| EA025504B1 (ru) * | 2012-09-26 | 2016-12-30 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | Молекулярное сито sapo-34 и способ его получения |
| US9744526B2 (en) | 2012-09-26 | 2017-08-29 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | SAPO-34 molecular sieve and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090062113A1 (en) | 2009-03-05 |
| US8815764B2 (en) | 2014-08-26 |
| CN101376111B (zh) | 2012-09-19 |
| RU2396116C2 (ru) | 2010-08-10 |
| RU2008135260A (ru) | 2008-12-27 |
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