CN102164856A - 一种制备分子筛珠的方法 - Google Patents
一种制备分子筛珠的方法 Download PDFInfo
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- CN102164856A CN102164856A CN2008801312709A CN200880131270A CN102164856A CN 102164856 A CN102164856 A CN 102164856A CN 2008801312709 A CN2008801312709 A CN 2008801312709A CN 200880131270 A CN200880131270 A CN 200880131270A CN 102164856 A CN102164856 A CN 102164856A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- 239000011324 bead Substances 0.000 title abstract 7
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000011541 reaction mixture Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 8
- 235000015097 nutrients Nutrition 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 42
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 230000009257 reactivity Effects 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000011049 pearl Substances 0.000 description 81
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 37
- 239000010457 zeolite Substances 0.000 description 37
- 229910021536 Zeolite Inorganic materials 0.000 description 36
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000012452 mother liquor Substances 0.000 description 15
- 235000019353 potassium silicate Nutrition 0.000 description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 description 14
- 239000004411 aluminium Substances 0.000 description 13
- 239000011162 core material Substances 0.000 description 13
- 239000010703 silicon Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 hydroxide compound Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004231 fluid catalytic cracking Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 102000007698 Alcohol dehydrogenase Human genes 0.000 description 1
- 108010021809 Alcohol dehydrogenase Proteins 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RZRNZDQNXWVZNY-UHFFFAOYSA-N [B].[B].[B].[Cr].[Cr].[Cr].[Cr].[Cr] Chemical compound [B].[B].[B].[Cr].[Cr].[Cr].[Cr].[Cr] RZRNZDQNXWVZNY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- YCLAMANSVUJYPT-UHFFFAOYSA-L aluminum chloride hydroxide hydrate Chemical compound O.[OH-].[Al+3].[Cl-] YCLAMANSVUJYPT-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000002520 cambial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 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 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- GPMKKHIGAJLBMZ-UHFFFAOYSA-J titanium(4+);tetraacetate Chemical compound [Ti+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GPMKKHIGAJLBMZ-UHFFFAOYSA-J 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
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Abstract
开发了一种制备各种组合物珠的方法。本方法涉及制备分子筛骨架元素来源的反应混合物。反应混合物可任选含有分子筛种子。加入骨架元素的另外来源以得到临界过饱和极限以上的浓度,从而形成珠。取决于反应混合物的组成和反应条件,可得到基本为无定形的珠至基本为结晶分子筛的珠。又可将这些珠进一步加工以在珠上沉积分子筛层。
Description
发明背景
本发明涉及一种制备包含无定形组分和任选结晶分子筛组分的分子筛珠的方法。本方法包括在反应条件下采用包含分子筛骨架元素的来源和任选分子筛颗粒的反应混合物,并将它以形成珠的速率和时间加入骨架元素的反应性来源中。
分子筛珠用于许多催化剂和吸附剂应用中。然而,用于制备珠的方法具有某些缺点。例如当使用喷雾干燥时,需要使用粘合剂以提供良好的强度,这又稀释了分子筛浓度。球粒形成技术也通常使用粘合剂并进一步具有最小尺寸限制。
还存在大量通过在内芯上沉积层而形成催化剂颗粒的参考文献。例如,US 4,283,583公开了由惰性芯和包含活性催化沸石材料的外涂层组成的涂覆沸石催化剂。该催化剂通过将部分干燥的内芯润湿,然后使芯与沸石粉接触而制备。US 4,482,774公开了具有结晶硅石多晶型物作为芯材料和具有基本上相同结晶结构的改性硅石覆盖层的复合沸石。覆盖层通过将预成型的硅石芯颗粒在结晶条件下加入结晶凝胶中,从而使沸石结晶在芯上而制备。US 4,088,605公开了在含铝沸石上生长基本无铝的壳。US 5,895,769公开了在多孔基质上沉积多晶沸石。US 5,935,889公开了通过用含涂料的雾化浆料涂覆芯颗粒而制备催化剂颗粒。最后,US 6,013,851公开了具有沉积于其上的表面层的芯沸石,其中表面层具有比芯更高的Si/Al比。
申请人已开发了制备分子筛珠的独特方法,其中将分子筛种子或颗粒在含分子筛骨架元素的反应性来源的溶液中浆化。向该浆料中以形成凝胶的速率和时间加入骨架元素来源并使凝胶和颗粒聚集成珠。珠可以被分离并包含结晶分子筛组分和无定形组分,所述无定形组分为分子筛前体。
发明概述
一种制备包含无定形和结晶分子筛组分的珠组合物的方法,所述结晶组分具有三维骨架和由以下经验式表示的骨架组成:
(ElwAlxPySiz)O2 (1)
其中El、Al、P和Si为作为四面体氧化物单元存在的骨架元素,“w”为El的摩尔分数且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0,且无定形组分的量为0-100重量%,所述方法包括在反应条件下提供包含基于等式(1)的El、Al、P和Si的反应性来源的反应混合物;向混合物中添加营养素以提供分子筛的骨架元素;进行添加以达到元素的临界过饱和浓度,从而形成珠,并持续进一步添加营养素以得到具有所需粒度的珠。
可将分离的珠进一步加热以将至少一部分无定形组分转化成结晶分子筛组分。
本发明另一实施方案为分离所述珠,将珠在反应混合物中浆化,以保持营养素浓度在饱和极限与临界过饱和极限之间的速率向混合物中加入营养素以在珠上生长分子筛层。
又一实施方案为由任何上述方法得到的产物。
本发明另一实施方案为上述分子筛珠在烃转化方法中的用途。
本发明这些和其它目的和实施方案将在以下本发明详述以后变得更清晰。
发明详述
本发明一个实施方案为一种制备包含至少无定形组分的珠组合物的方法。无定形组分为分子筛的前体。珠的其它组分可以为分子筛组分和结晶氧化铝。本方法包括形成包含分子筛组分元素的反应性来源和任选分子筛组分种子的反应混合物。分子筛组分可以为具有三维骨架且具有结晶均匀孔的任何分子筛。这些筛被分类为沸石或非沸石分子筛。沸石为其中骨架结构由SiO2和AlO2四面体氧化物组成的铝硅酸盐组合物。非沸石分子筛为含有不同于铝和硅的元素的那些。实例包括硅铝磷酸盐和铝磷酸盐分子筛。可使用本发明方法制备的沸石和非沸石分子筛具有三维骨架结构和以下经验通式表示的骨架组成:
(ElwAlxPySiz)O2 (1)
其中El为能形成如下所述三维骨架(四面体)氧化物单元的元素,且P、Al和Si也是作为四面体氧化物单元存在的骨架元素。El的摩尔分数由“w”表示且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0。当“El”包含两种或更多种元素时,“w”表示所述元素(El1、El2、El3、El4等)的摩尔分数且“w”等于分别表示El1、El2、El3、El4等的摩尔分数的“w1”、“w2”、“w3”、“w4”等之和。这些分子筛简称为EIAPSO并详细描述于US 4,793,984中,将其全部内容引入作为参考。El元素的选择标准也显示于’984专利中。El通过至少一个以下标准表征:
1)“El”通过选自d0、d1、d2、d5、d6、d7或d10的电子轨道构型表征,其中金属配体“-O-El”的小晶体场稳定能有利于元素El与O2-的四面体配位,如“无机化学(Inorganic Chemistry)”J.E.Huheey,Harper Row,第348页(1978)中讨论的;
2)“El”的特征为能够在水溶液中形成稳定的含氧或含羟物质(oxo or hydroxo species),如通过大于10-14的第一水解常数K11证明,如“阳离子的水解(The Hydrolysis of Cations)”,C.F.Baes和R.E.Mesmer,John Wiley & Sons(1976)中讨论的;
3)“El”选自已知存在于与不同硅石改性、石英、方石英或鳞石英几何相关的晶体结构类型中的元素,如E.Parthe,“Crystal Chemistry of Tetrahedral Structures”,Gordon and Breach,New York,London,第66-68页(1964)中讨论的;和
4)“El”为其阳离子形式由Pearson.(J.E.Huheey,“无机化学(Inorganic Chemistry)”,Harper & Row,第276页(1978)分类为“硬”或“边缘”酸的元素,其与“硬”碱O2-相互作用形成比分类为“软”酸的阳离子更稳定的键。具体元素包括但不限于砷、铍、硼、铬、钴、镍、镓、锗、铁、锂、镁、锰、钛、钒、锡和锌。
从上述通式看,可描述和制备几类分子筛。例如,当“w”和“y”都为0时,分子筛为沸石或沸石类分子筛。在这种情况下式(1)变为:
(AlxSi1-x)O2 (2)
其中x的值为0-0.5。沸石的具体实例包括但不限于沸石A、沸石X、丝光沸石、硅沸石(silicalite)、沸石β、沸石Y、沸石L、ZSM-12、UZM-4和UZM-5。UZM-4和UZM-5分别描述于US 6,419,895B1和US 6,613,302B1中,将其全部内容引入作为参考。当x为0时,沸石为硅沸石。在式(1)中的“x”大于0的情况下得到式(3):
(ElwAlx’PySiz)O2 (3)
其中“w”、“y”和“z”如式(1)中定义,x’的值为大于0至0.5。另外,当式(3)中的“w”和“z”为0时,或当式(1)中的“w”和“z”为0且“x”大于0时,得到ALPO类非沸石类分子筛,其详细描述于US 4,310,440和US 4,500,651中,将二者全部内容引入作为参考。另外,当式(1)或(3)中的“w”为0且“z”大于0(且式(1)中“x”大于0)时,则得到SAPO类非沸石类分子筛,其非限定性实例为US 4,440,871中所述SAPO-34和SAPO-11,将其全部内容引入作为参考。当式(1)或(3)中的“z”为0且所有其他下标大于0时,具有EIAPO类非沸石类分子筛。最后当式(1)或(3)中所有下标大于0时,具有上述EIAPSO类非沸石类分子筛,其一个实例为MAPSO-31。
分子筛种子(其为任选组分)通过本领域已知的方法制备,基本包括制备包含El、Al、Si和P的反应性来源以及一种或多种模板剂/结构导向剂和水的反应混合物,使它在使分子筛结晶的温度和时间下,通常在自生压力下反应。可使用的模板剂(templating agent)是本领域中熟知的,包括但不限于碱金属、碱土金属和有机化合物。有机化合物为任何本领域熟知的那些,包括但不限于胺类如哌啶、三丙胺、二丙胺、二乙醇胺、三乙醇胺、环己胺,和季铵化合物如四甲基铵、四丁基铵、四乙基铵、四丙基铵、乙基三甲基铵、二乙基二甲基铵等的卤化物或氢氧化物化合物。根据本领域中熟知的,铝的来源包括但不限于烷醇铝、假勃姆石、三水铝石、胶体氧化铝、氧化铝溶胶、铝酸钠、三氯化铝和水合氯化铝(aluminum chlorohydrate)。在以上中,优选的铝源为假勃姆石、铝酸钠和烷醇铝如异丙醇铝。硅源包括但不限于硅溶胶、胶态氧化硅、火成氧化硅、硅胶、烷醇硅、硅酸和碱金属硅酸盐如硅酸钠。磷源包括但不限于磷酸和有机磷酸盐如三乙基磷酸盐。
元素“El”的来源可以为允许原位形成元素的反应性形式,即呈反应性以形成元素“El”的骨架氧化物单元的任何形式。可使用的元素“El”的化合物包括氧化物、氢氧化物、醇盐、硝酸盐、硫酸盐、卤化物、羧酸盐及其混合物。可使用的代表性化合物包括但不限于:砷和铍的羧酸盐;氯化钴六水合物、α碘化钴;硫酸钴;乙酸钴;溴化钴;氯化钴;烷醇硼;乙酸铬;烷醇镓;乙酸锌;溴化锌;甲酸锌;碘化锌;硫酸锌七水合物;二氧化锗;乙酸铁(II);乙酸锂;乙酸镁;溴化镁;氯化镁;碘化镁;硝酸镁;硫酸镁;乙酸锰;溴化锰;硫酸锰;四氯化钛;羧酸钛;乙酸钛;乙酸锌;氯化锡等。
产生的反应混合物现在在70-200℃的温度和1-144小时下通常在自生压力下反应,从而结晶所需分子筛。将分子筛颗粒通过常规技术如过滤、离心等分离,并干燥以得到粉末。该分子筛粉现在可用作制备进行本发明方法的反应混合物中的任选组分的种子或颗粒。
首先考察其中不添加种子的实施方案,反应混合物包含相应于等式(1)的El、Al、P和Si的反应性来源。反应混合物还任选含有模板剂和酸或碱的来源以将pH调整至所需范围。
现在向产生的浆料或反应混合物中加入所需骨架元素的来源,下文称作营养素。因此,加入的营养素或营养素组合为任何可形成分子筛的那些。这些组合包括但不限于:1)硅源;2)铝和硅源;3)铝、磷和硅源;4)铝和磷源;5)El和硅源;6)El、铝和磷源;和7)El、铝、硅和磷源。还应指出可需要加入其他模板剂/结构导向剂。这可通过与一种营养素一起添加所需试剂源或作为单独料流添加所需试剂源而进行。另外,初始反应混合物可含有过量所需模板剂。
不管营养素的选择,它们可通过任何常规方法加入。这些方法包括制备营养素的溶液,制备固体悬浮液或浆料,直接加入固体和加入纯营养素。当然一种营养素可通过一种方法加入,而其他营养素可通过另一种方法加入。另外,取决于具体营养素,可需要加入其他酸或碱以达到所需pH。例如当硅酸钠用作营养素或硅源时,可需要加入酸以中和可产生的氢氧化钠。
当加入大于一种营养素如Si和Al时,它们可同时或顺序添加。通过使用顺序添加,在液体或浆料的情况下仅需要使用一个泵。同时添加可以以两种方式中一种进行。第一,使用单独的口或注射器将各营养素供入含反应混合物的反应器中。第二,可将各营养素供入接受罐中,混合,然后作为一个料流供入含种子浆料的反应器中。后一种方法是优选的。最后,营养素可连续或间歇式添加。如果是间歇式,则添加可以是规则间隔或不规则间隔的。
添加在环境温度至80℃的温度下进行。在环境至80℃的温度下(优选环境温度),优选连续进行添加直至营养素浓度为形成珠的临界过饱和浓度以上。可连续添加直至得到具有所需粒度的珠。如果没有添加种子且添加在分子筛结晶温度以下,优选在环境温度下进行,则珠为基本100%无定形的。这些珠称为第一珠组合物。如所述,初始反应混合物还可含有具有相同组成的分子筛种子,其由混合物中的反应性来源产生。在这种情况下,在添加过程结束时产生的珠具有无定形组分和结晶分子筛组分的混合物。在本方法开始时存在的种子材料的量可广泛地为反应混合物的0.1-20重量%。种子也可任选在添加营养素期间周期性加入以得到较大的珠并控制粒度分布。这些珠称为第二珠组合物。
也可将具有或不具有种子的反应混合物加热至反应温度,该温度为所需分子筛结晶温度或以上。该温度通常为70-200℃。在这些条件下,优选脉冲添加营养素直至它们的浓度达到临界过饱和极限以上。在该点,开始结晶并形成珠。在本方法期间可再次周期性加入种子以生长更大的珠和/或控制珠大小。另外,在完成营养素的添加以后,可将混合物保持在反应温度下1-144小时以进一步结晶分子筛组分。还发现当铝为一种骨架元素时,在结晶温度或以上形成的珠还含有量为珠的0-60重量%的结晶氧化铝。这些珠称为第三珠组合物。
可通过采用最终反应混合物并将它加热至结晶温度并保持该混合物在该温度下以结晶至少一部分无定形组分而进一步加工第一或第二珠组合物。温度为70-200℃,时间为1-144小时。
不管如何制备珠,它们可具有可在100%无定形组分至100%结晶分子筛组分变化的组成。因此,取决于应用,无定形含量可以为0-100重量%,优选0-50重量%,最优选0-20重量%。结晶分子筛组分同样可以以0-100重量%,但优选15-100重量%,最优选80-100重量%存在。如果还存在结晶氧化铝,则它以大于0-60重量%,但通常为5-15重量%的量存在。不管如何制备珠,理想的是进行该方法以得到平均粒度为10-800μm,优选20-300μm,最优选30-200μm的珠。粒度通过常规技术测定。
第一、第二和第三珠组合物可例如用作催化金属的载体,例如作为催化剂和吸附剂,但是不是所有组合物都可用于所有应用。然而,优选的用途是作为芯,在其上沉积一层或多层分子筛或其他无机氧化物层。具体分子筛的层可使用上述基本方法生长或沉积在以上珠上。即,反应混合物由珠、El、Al、P和Si的来源、其它碱或酸和模板剂制备。在一个实施方案中,最终反应混合物可充当该具体方法的起始反应混合物。作为选择,可将珠分离,然后在包含所需元素来源、模板剂等的混合物中浆化。层可包含与芯元素相同的元素或不同的元素(至少一种)。另外,分子筛层可具有相同或不同的结构。
该方法的反应条件包括70-200℃的温度和自生压力。在这些条件下,无定形组分(如果有的话)开始结晶。接着连续或间歇式添加营养素。当连续添加时,将营养素浓度保持在临界过饱和以下但在饱和浓度以上。在这种情况下,珠外表面上的分子筛晶体开始生长,从而形成分子筛层。控制营养素添加速率使得它基本上与晶体生长速率相同。晶体生长速率使用分析技术如扫描电子显微镜(SEM)经验性测定。控制连续添加速率的另一途径是测量并保持各营养素的浓度在饱和浓度与临界过饱和浓度之间。进行连续添加一段时间直至层具有所需厚度。最后,如当分子筛珠的结构与层相同时所述进行连续添加。然而,两种分子筛可具有不同的组成,例如SAPO-34和ALPO-34。为促进层的生长,可在该方法中间歇式添加分子筛种子晶体。
本发明还有一个实施方案采用在反应温度下的反应混合物并间歇式添加营养素。进行该添加直至营养素的浓度为临界过饱和浓度以上并发生成核,从而形成分子筛晶体,其聚集在珠上并在芯上形成层。在这种情况下,结晶的分子筛不必须具有与珠分子筛相同的结构。通常脉冲或间歇式添加期间以后是如上所述连续添加期间,以生长分子筛晶体,其在珠上形成层。在脉冲和/或连续添加期间,也可加入分子筛种子。通常添加脉冲可持续1秒至5分钟,各脉冲之间的时间为10秒至3小时。连续添加通常进行1-144小时。间歇式和连续添加可重复多次,但至少2次,条件是最后步骤为连续添加。
在所有上述各个实施方案中,优选将剪切力引入反应混合物中以控制混合物的聚集和均匀性。剪切力可通过机械手段、水力手段等施加。施加剪切力的具体方法包括但不限于搅拌器、叶轮、超声、对撞射流等。控制剪切力的量使得不发生过量聚集但在形成层的情况下剪切力不会太大而弄断由珠形成的层。
分层分子筛珠或第四珠组合物可用于各种方法中,包括但不限于吸附、烃转化方法中的催化剂或催化剂载体。烃转化方法是本领域中熟知的,包括开环、裂化、加氢裂化、芳族烃和异链烷烃的烷基化、异构化、聚合、重整、脱蜡、氢化、脱氢、烷基转移、脱烷基化、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲烷化和合成气轮换法。可用于这些方法中的具体反应条件和进料类型陈述于US 4,310,440和US 4,440,871中,将其引入作为参考。
加氢裂化条件通常包括400-1200°F(204-649℃),优选600-950°F(316-510℃)的温度。反应压力为大气压至3,500psig(24,132kPa),优选200-300psig(1379-20,685kPa)。接触时间通常对应于0.1-15hr-1,优选0.2-3hr-1的液时空速度(LHSV)。氢循环速率为1,000-50,000标准立方英尺(scf)每桶进料(178-8,888std.m3/m3),优选2,000-30,000scf每桶进料(355-5,333std.m3/m3)。合适的加氢处理条件通常在上述加氢裂化条件的宽范围内。
通常将反应区流出物从催化剂床中取出,进行部分冷凝和蒸气-液体分离,然后分馏以回收其各个组分。使氢气和如果需要的话一些或所有未转化的较重材料再循环至反应器。作为选择,可使用两段流动,其中未转化材料进入第二反应器中。本发明催化剂可只在该方法的一段中使用或可在两个反应器段中使用。
催化裂化方法优选使用进料如瓦斯油、重石脑油、脱沥青原油残油等进行,其中汽油为主要理想产物。850-1100°F(454-593℃)的温度条件、0.5-10hr-1的LHSV值和0-50psig(0-345kPa)的压力条件是合适的。
芳族烃的烷基化通常包括使芳族烃,尤其是苯与单烯烃(C2-C12)反应以制备线性烷基取代的芳族烃。该方法在5∶1-30∶1的芳族烃:烯烃(例如苯:烯烃)比、0.3-6hr-1的LHSV值、100-250℃的温度和200-1000psig(1379-6895kPa)的压力下进行。关于设备的其他详情可在US4,870,222中找到,将其引入作为参考。
将异链烷烃用烯烃烷基化以制备适用作发动机燃料组分的烷基化物在-30℃至40℃的温度、大气压至6,894kPa(1,000psig)的压力和0.1-120hr-1的重时空速(WHSV)下进行。关于链烷烃烷基化的详情可在US 5,157,196和US 5,157,197中找到,将其引入作为参考。
其他反应可通过这些层状组合物催化,包括碱催化的烷基芳族烃侧链烷基化、醛醇缩合、烯烃双键异构化和乙炔异构化、醇脱氢和烯烃二聚、低聚和醇转化成烯烃。这些材料的适当离子交换形式可在汽车和工业排气流中催化NOx还原成N2。可用于这些方法中的一些反应条件和进料类型陈述于US 5,015,796和H.Pines,The Chemistry of Catalytic Hydrocarbon Conversions,Academic Press(1981),第123-154页和其中所含的参考文件中,将其引入作为参考。
尤其优选的珠组合物为其中珠芯含有用或不用种子制备的沸石Y且层也是沸石Y的第四珠组合物。这些沸石Y珠组合物特别用于裂化或加氢裂化,特别是流化催化裂化(FCC)中。FCC装置和方法是本领域熟知的,并且在上述催化裂化条件下进行。另外,催化剂为催化剂颗粒的移动床。描述FCC的专利的实例包括US 3,838,036和US 4,064,038,将其全部内容引入作为参考。
陈述以下实施例以阐明本发明。应当理解该实施例仅用于阐述,不意欲作为对附属权利要求中所述本发明宽范围的不当限制。
实施例1
向5L容器中加入220g沸石Y(Si/Al2=5且平均粒度为1.0μm)种子和1541g具有组成(在H2O中12.4重量%Si、0.21重量%Al和9.0重量%Na)的再循环母液溶液并将混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)和铝酸钠(24重量%Al2O3和20重量%Na2O)的水溶液以下表所示增加的脉冲长度加入容器中。
脉冲时间(s) | 间隔时间(min) | 硅酸盐进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) |
62 | 15 | 4750 | 975 |
64 | 15 | 4750 | 975 |
66 | 15 | 4750 | 975 |
68 | 15 | 4750 | 975 |
70 | 15 | 4750 | 975 |
72 | 15 | 4750 | 975 |
74 | 15 | 4750 | 975 |
76 | 15 | 4750 | 975 |
78 | 15 | 4750 | 975 |
在脉冲添加顺序结束时,使用1224.1mL相同硅酸钠和251.3mL相同铝酸钠溶液以恒定速率经146分钟进行营养素的连续添加。在营养素添加以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为244.5g分级珠。珠为在75℃下与10%硝酸铵溶液交换3次的铵离子。将交换的珠在600℃下在50%蒸汽中蒸2小时,然后再交换。X射线衍射分析显示产物为具有三水铝石结晶杂质的24.5%Y沸石。最后,分级产物的化学分析显示Si/Al2比为0.37。
实施例2
向5L容器中加入220g沸石Y(Si/Al2=5且平均粒度为1.0μm)种子和1541g具有组成(在H2O中12.4重量%Si、0.21重量%Al和9.0重量%Na)的再循环母液溶液并将混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)和铝酸钠(24重量%Al2O3和20重量%Na2O)的水溶液以下表所示增加的脉冲长度加入容器中。
脉冲时间(s) | 间隔时间(min) | 硅酸盐进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) |
62 | 15 | 4750 | 650 |
64 | 15 | 4750 | 650 |
66 | 15 | 4750 | 650 |
68 | 15 | 4750 | 650 |
70 | 15 | 4750 | 650 |
72 | 15 | 4750 | 650 |
74 | 15 | 4750 | 650 |
76 | 15 | 4750 | 650 |
78 | 15 | 4750 | 650 |
在脉冲添加顺序结束时,使用1224.1mL相同硅酸钠和167.6mL相同铝酸钠溶液以恒定速率经146分钟进行营养素的连续添加。在营养素添加以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为150.5g分级珠。
向2L容器中加入70g沸石Y种子、416.2g具有分析(在H2O中4.76重量%Si、0.06重量%Al和3.72重量%Na)的再循环母液溶液和80g分级珠,将该混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)、铝酸钠(24重量%Al2O3和20重量%Na2O)和稀LudoxTMAS40(23.8重量%SiO2)的水溶液以下表所示提高的速率加入容器中。
时间(hr) | 硅酸钠进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) | LudoxTMAS40进料速率(mL/hr) |
0 | 13.9 | 7.5 | 24.1 |
1.25 | 16.6 | 9.0 | 29.0 |
2.5 | 19.6 | 10.6 | 34.2 |
3.75 | 22.9 | 12.4 | 39.9 |
5.0 | 26.4 | 14.3 | 46.0 |
在营养素添加以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为130.5g分级珠。
将80g分级珠加回具有70g沸石Y种子和416.4g再循环母液的反应器中,并重复相同的程序。然后再次重复该程序,在初始珠上产生3层涂层。最终收率为94.5g分级珠。珠为在75℃下在淘析塔中与3.5L 10%硝酸铵溶液交换的铵离子。将交换的珠在600℃下在50%蒸汽中蒸2小时,然后再交换。X射线衍射分析显示产物为具有少量三水铝石结晶杂质的38.7%Y沸石。最后,分级产物的化学分析显示Si/Al2比为2.7。
实施例3
向250mL烧杯中加入1.0g沸石Y(Si/Al2=5)粉和50.0g 2.0重量%NaOH水溶液。将烧杯的内容物搅拌,同时分别以10mL/hr、30mL/hr和180mL/hr连续加入铝酸钠、硅酸钠和去离子水。在50分钟以后加入另外0.5g沸石Y粉以促进进一步聚集。在另外2小时以后,关闭进料,将固体从母液中过滤以得到42g珠,发现该珠具有分子筛组分和无定形组分。平均粒径通常为50μm,粒度分布为1-150μm。
实施例4
向2L容器中加入80g平均粒度为70μm的α氧化铝芯(VersalTM 900)、88g沸石Y种子(Si/Al2=5且平均粒度为1.0μm)和616.4g具有分析(在H2O中12.4重量%Si、0.21重量%Al和9.0重量%Na)的再循环母液溶液,将该混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)和铝酸钠(24重量%Al2O3和20重量%Na2O)的水溶液以下表所示增加的脉冲长度加入容器中。
脉冲时间(s) | 间隔时间(min) | 硅酸盐进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) |
31 | 15 | 3800 | 520 |
32 | 15 | 3800 | 520 |
33 | 15 | 3800 | 520 |
34 | 15 | 3800 | 520 |
35 | 15 | 3800 | 520 |
36 | 15 | 3800 | 520 |
37 | 15 | 3800 | 520 |
38 | 15 | 3800 | 520 |
39 | 15 | 3800 | 520 |
在脉冲添加顺序结束时,使用455.6mL相同硅酸钠和62.3mL相同铝酸钠溶液以恒定速率经146分钟进行营养素的连续添加。在营养素加入以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为70.0g分级珠。
向2L容器中加入88g沸石Y种子、616.4g具有分析(在H2O中4.76重量%Si、0.06重量%Al和3.72重量%Na)的再循环母液溶液和65g分级珠,将该混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)和铝酸钠(24重量%Al2O3和20重量%Na2O)的水溶液加入或显示于下表中。
脉冲时间(s) | 间隔时间(min) | 硅酸盐进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) |
31 | 15 | 3800 | 520 |
32 | 15 | 3800 | 520 |
33 | 15 | 3800 | 520 |
34 | 15 | 3800 | 520 |
35 | 15 | 3800 | 520 |
36 | 15 | 3800 | 520 |
37 | 15 | 3800 | 520 |
38 | 15 | 3800 | 520 |
39 | 15 | 3800 | 520 |
40 | 15 | 3800 | 520 |
41 | 15 | 3800 | 520 |
42 | 15 | 3800 | 520 |
43 | 15 | 3800 | 520 |
在脉冲加入顺序结束时,使用241.7mL相同硅酸钠和33.1mL相同铝酸钠溶液以恒定速率经78.5分钟进行营养素的连续加入。在营养素加入以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为84.9g分级珠。
使用80g分级珠与88g沸石Y种子和616.4g再循环母液重复以上程序。收率为95.1g分级珠。
向反应器中加入上段的80g分级珠、88g沸石Y种子和616.4g再循环母液,将该混合物加热至95℃,同时搅拌。将硅酸钠(29重量%SiO2和9重量%Na2O)和铝酸钠(24重量%Al2O3和20重量%Na2O)的水溶液以下表所示增加的脉冲长度加入容器中。
脉冲时间(s) | 间隔时间(min) | 硅酸盐进料速率(mL/hr) | 铝酸盐进料速率(mL/hr) |
31 | 15 | 3800 | 520 |
32 | 15 | 3800 | 520 |
33 | 15 | 3800 | 520 |
34 | 15 | 3800 | 520 |
35 | 15 | 3800 | 520 |
36 | 15 | 3800 | 520 |
37 | 15 | 3800 | 520 |
38 | 15 | 3800 | 520 |
39 | 15 | 3800 | 520 |
在脉冲加入顺序结束时,使用455.6mL相同硅酸钠和62.3mL相同铝酸钠溶液以恒定速率经146分钟进行营养素的连续加入。在营养素加入以后,将产物过滤,洗涤,然后在室温下干燥。保留母液以再循环。将固体洗涤、筛分并淘析以保留20-150μm之间的珠。收率为99.4g分级珠。
该珠为在75℃下与10%硝酸铵溶液交换的铵离子。将交换的珠在600℃下在50%蒸汽中蒸2小时,然后再交换。
Claims (10)
1.一种制备包含无定形组分和结晶分子筛组分的珠组合物的方法,所述结晶组分具有三维骨架和由以下经验式表示的骨架组成:
(ElwAlxPySiz)O2 (1)
其中El、Al、P和Si为作为四面体氧化物单元存在的骨架元素,“w”为El的摩尔分数且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0,且无定形组分的量为0-100重量%,所述方法包括在环境温度至70℃的温度和自生压力下提供包含基于等式(1)的El、Al、P和Si的反应性来源的反应混合物;向混合物中添加基于等式(1)的营养素;进行添加以达到元素的临界过饱和浓度,从而形成珠,并持续进一步添加营养素以得到具有所需粒度的珠。
2.根据权利要求1的方法,其中所述反应混合物还包含对应于反应混合物中El、Al、P和Si元素的分子筛种子。
3.根据权利要求1或2的方法,其中所述珠包含100重量%无定形组分,将珠和反应混合物加热至70-200℃的温度保持足够的时间以将至少一部分无定形组分转化成结晶分子筛组分。
4.根据权利要求1的方法,其中所述珠的平均粒度为10-800μm。
5.一种制备包含具有三维骨架和由以下经验式表示的骨架组成的结晶分子筛组分的分子筛珠的方法:
(ElwAlxPySiz)O2 (1)
其中El、Al、P和Si为作为四面体氧化物单元存在的骨架元素,“w”为El的摩尔分数且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0,所述方法包括在反应条件,包括70-200℃的温度和自生压力下提供包含基于等式(1)的El、Al、P和Si的反应性来源和种子珠的反应混合物,其中种子珠包含无定形组分和具有基于等式(1)的组成的结晶分子筛组分,且其中无定形组分以0-100%的量存在;向混合物中添加基于等式(1)的营养素以提供分子筛的骨架元素;以保持饱和极限与临界过饱和极限之间的营养素浓度的速率和使珠生长至所需大小的时间进行添加。
6.包含无定形组分和结晶分子筛组分的珠组合物,所述结晶组分具有三维骨架和由以下经验式表示的骨架组成:
(ElwAlxPySiz)O2 (1)
其中El、Al、P和Si为作为四面体氧化物单元存在的骨架元素,“w”为El的摩尔分数且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0,所述无定形组分以0-100重量%的量存在,且所述珠的平均粒度为10-800μm。
7.权利要求6的组合物,其中“w”和“y”都为0。
8.根据权利要求6的组合物,其还包含分布在整个珠中的氧化铝组分。
9.根据权利要求6的组合物,其还在珠上包含分子筛层,所述分子筛具有与珠中分子筛组分相同的组成和结构。
10.一种烃转化方法,其包括使烃与催化剂在烃转化条件下接触以得到转化产物,所述催化剂包含含有无定形组分和结晶分子筛组分的珠组合物,所述结晶组分具有三维骨架和由以下经验式表示的骨架组成:
(ElwAlxPySiz)O2 (1)
其中El、Al、P和Si为作为四面体氧化物单元存在的骨架元素,“w”为El的摩尔分数且值为0-0.5,“x”为Al的摩尔分数且值为0-0.5,“y”为P的摩尔分数且值为0-0.5,“z”为Si的摩尔分数且值为0-1,w+x+y+z=1,且“y”和“z”不同时为0,所述分子筛组分以15-100重量%的量存在。
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