TW201533231A - 一種氫化裂解催化劑及用途 - Google Patents
一種氫化裂解催化劑及用途 Download PDFInfo
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- TW201533231A TW201533231A TW104105737A TW104105737A TW201533231A TW 201533231 A TW201533231 A TW 201533231A TW 104105737 A TW104105737 A TW 104105737A TW 104105737 A TW104105737 A TW 104105737A TW 201533231 A TW201533231 A TW 201533231A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 8
- 238000005336 cracking Methods 0.000 title abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 11
- 238000001228 spectrum Methods 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 46
- 239000010457 zeolite Substances 0.000 claims description 43
- 229910021536 Zeolite Inorganic materials 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 40
- 239000002808 molecular sieve Substances 0.000 claims description 23
- 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 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 16
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- LEHUDBPYSAPFFO-UHFFFAOYSA-N alumane;bismuth Chemical compound [AlH3].[Bi] LEHUDBPYSAPFFO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 238000004566 IR spectroscopy Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- UZQSJWBBQOJUOT-UHFFFAOYSA-N alumane;lanthanum Chemical compound [AlH3].[La] UZQSJWBBQOJUOT-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 23
- 238000001354 calcination Methods 0.000 abstract description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 3
- 238000012512 characterization method Methods 0.000 abstract 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 2
- 238000002329 infrared spectrum Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 13
- 235000015165 citric acid Nutrition 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000006259 organic additive Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 241000640882 Condea Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- -1 VIB metal compound Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012013 faujasite Substances 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 102000007641 Trefoil Factors Human genes 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
一種氫化裂解催化劑,含有載體和至少一種選自Ⅷ族和至少一種選自VIB族的金屬組份,所述載體含有酸性矽鋁組份和源自於擬薄水鋁石組份的氧化鋁,以.載體為基準,酸性矽鋁組份的含量為3-80重量%,源自於擬薄水鋁石組份的氧化鋁的含量為20-95重量%,其特徵在於,所述載體由酸性矽鋁組份與擬薄水鋁石組份混合、成型、乾燥並煅燒得到,所述擬薄水鋁石組份包括擬薄水鋁石PB1和擬薄水鋁石PB2,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為0-60重量%,以X光繞射表徵,所述PB1的κ1和κ2分別大於1至小於等於3,其中,κ1=h2/h1、κ2=h3/h2,h1、h2和h3分別為PB1的X光繞射譜圖中在2 θ角為24-30°、35-41°和46-52°的三個繞射峰的峰高,以紅外光譜表徵,PB2的δ值為1.5-4.5,其中,δ=I1/(I2+I3),I1為PB2的紅外羥基譜中3665-3680cm-1處吸收峰的峰高,I2為3720-3730cm-1處吸收峰的峰高,I3為3760-3780cm-1處吸收峰的峰高。
Description
本發明涉及一種氫化裂解催化劑及其用途。
工業氫化裂解進料包括VGO等350-540℃餾份,反應溫度一般在350-440℃之間。進料中高沸點組份在反應時以液體形式同催化劑進行接觸。催化劑孔道結構就具有更重要的作用。需要增加載體的孔徑,以提高反應物分子接觸到催化劑內氫化活性金屬的能力。分子篩和金屬硫化物孔體積較小,特別是滿足石油加工所要求大分子烴類進料要求的中大孔較少。傳統可通過在氫化裂解催化劑載體中引入大孔體積耐熱無機氧化物基質的方法來改性,例如引入氧化鋁基質。
ZL97121663.0公開了一種特別適用於生產中間餾份油的氫化裂解催化劑,含有無定形矽鋁組份和小孔氧化鋁粘合劑作為載體,以及至少一種VIB族元素和至少一種Ⅷ族元素作為氫化金屬,其中無定形矽鋁組份的含量為30-60重量%,氫化金屬以氧化物計的總含量為20-35重量%,餘量為小孔氧化鋁粘合劑,其特徵在於催化劑比表面150-300米2/克,孔體積0.25-0.50毫升/克,4-15奈米孔分佈在60-90%,
紅外酸度0.30-0.50毫摩爾/克。
ZL01123765.1公開了一種柴油氫化處理催化劑。該催化劑含有一種載體和負載在該載體上的鉬和/或鎢及鎳和/或鈷,其特徵在於,所述載體由氧化鋁和沸石組成,氧化鋁與沸石的重量比為90:10-50:50,所述氧化鋁是由小孔氧化鋁和大孔氧化鋁按照75:25-50:50的重量比複合而成的氧化鋁,其中,小孔氧化鋁為直徑小於80埃孔的孔體積占總孔體積95%以上的氧化鋁,大孔氧化鋁為直徑60-600埃孔的孔體積占總孔體積70%以上的氧化鋁。
本發明的目的是提供一種性能得到改性了的氫化裂解催化劑以及該催化劑應用。
本發明涉及的內容包括:
1.一種氫化裂解催化劑,含有載體和至少一種選自Ⅷ族和至少一種選自VIB族的金屬組份,所述載體含有酸性矽鋁組份和源自於擬薄水鋁石組份的氧化鋁,以載體為基準,酸性矽鋁組份的含量為3-80重量%,源自於擬薄水鋁石組份的氧化鋁的含量為20-95重量%,其特徵在於,所述載體由酸性矽鋁組份與擬薄水鋁石組份混合、成型、乾燥並煅燒得到,所述擬薄水鋁石組份包括擬薄水鋁石PB1和擬薄水鋁石PB2,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為0-60重量%,以X光繞射表徵,所述PB1的κ
1和κ2分別大於1至小於等於3,其中,κ1=h2/h1、κ2=h3/h2,h1、h2和h3分別為PB1的X光繞射譜圖中在2 θ角為24-30°、35-41°和46-52°的三個繞射峰的峰高,以紅外光譜表徵,PB2的δ值為1.5-4.5,其中,δ=I1/(I2+I3),I1為PB2的紅外羥基譜中3665-3680cm-1處吸收峰的峰高,I2為3720-3730cm-1處吸收峰的峰高,I3為3760-3780cm-1處吸收峰的峰高。
2.根據1所述的催化劑,其特徵在於,以載體為基準,酸性矽鋁組份的含量為5-65重量%,源自於擬薄水鋁石組份的氧化鋁的含量為30-90重量%。
3.根據前述任一項所述的催化劑,其特徵在於,以X光繞射表徵,所述PB1的κ1和κ2分別為1.02-2.4,優選所述PB1的κ1為1.2-2.3,κ2為1.02-1.4。
4.根據前述任一項所述的催化劑,其特徵在於,所述PB1的比表面積為100-350米2/克,孔體積為0.7-1.2毫升/克。
5.根據前述任一項所述的催化劑,其特徵在於,所述PB1的比表面積為150-280米2/克,孔體積為0.85-1.12毫升/克。
6.按照前述任一項所述的催化劑,其特徵在於,所述酸性矽鋁組份包括沸石和/或無定形矽鋁。
7.按照6所述的催化劑,其特徵在於,所述沸石選自具有八面沸石結構的沸石、具有Beta沸石結構的沸石或具有絲光沸石結構的沸石中的一種或幾種。
8.按照7所述的催化劑,其特徵在於,所述沸石選自HY沸石、稀土型Y沸石(REY)、稀土型HY沸石(REHY)、超穩Y沸石(USY)、稀土型超穩Y沸石(REUSY)、脫鋁Y
型沸石中的一種或幾種Y型分子篩。
9.根據8所述的催化劑,其特徵在於,所述Y型分子篩為超穩Y分子篩。
10.根據9所述的催化劑,其特徵在於,所述Y型分子篩的單元胞穴尺寸為2.460-2.430nm,比表面積為550-700米2/克,孔體積為0.30-0.45毫升/克。
11.根據8-10任一項所述的催化劑,其特徵在於,所述Y型分子篩含有磷,以所述分子篩為基準,磷的含量為0.1-2.5重量%。
12.根據11所述的催化劑,其特徵在於,以所述分子篩為基準,所述磷的含量為0.4-2.0重量%。
13.根據6所述的催化劑,其特徵在於,以所述無定形矽鋁為基準,其氧化矽的含量為10-80重量%,優選為15-55重量%。
14.根據6所述的催化劑,其特徵在於,所述無定形矽鋁的比表面積為350-750米2/克,孔體積為0.4-1.2毫升/克;優選比表面積為400-650米2/克,孔體積為0.45-0.95毫升/克。
15.根據前述任一項所述的催化劑,其特徵在於,所述Ⅷ族的金屬組份選自鎳和/或鈷,所述VIB族的金屬組份選自鉬/或鎢,以氧化物計並以所述催化劑為基準,所述鎳和/或鈷的含量為1-15重量%,所述鉬/或鎢的含量為5-40重量%。
16.根據15所述的催化劑,其特徵在於,以氧化物計並以所述催化劑為基準,所述鎳和/或鈷的含量為2.0-10重量%,所述鉬/或鎢的含量為10-35重量%。
17.根據前述任一項所述的催化劑,其特徵在於,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為5-60重量%;優選,以乾基計並以載體為基準,PB1的含量為20-80重量%,PB2的含量為10-50重量%。
18.根據前述任一項所述的催化劑,其特徵在於,所述PB2的δ值為1.8-3.8。
19.根據前述任一項所述的催化劑,其特徵在於,所述的乾燥條件包括:溫度為50-350℃,時間為1-24小時;所述的煅燒條件包括:溫度為400-700℃,時間為0.5-6小時。
20.根據前述任一項所述的催化劑,其特徵在於,所述的乾燥條件包括:溫度為80-200℃,時間為1-6小時;所述的煅燒條件包括:溫度為550-650℃,時間為1-3小時。
21.根據前述任一項所述的催化劑,其特徵在於,所述PB2為PB1於70-400℃乾燥0.5-14小時的改性物。
22.根據前述任一項所述的催化劑,其特徵在於,所述PB2為PB1於220-330℃乾燥1-6小時的改性物。
23.根據1-22任一項所述的催化劑在烴油加工中的應用。
在一個實施方案中,所述酸性矽鋁組份包括無定形矽鋁。本發明中,所述無定形矽鋁可以是市售的商品或採用任意一種現有技術製備。優選比表面積為350-750米2/克,孔體積為0.4-1.2毫升/克的無定形矽鋁,進一步優選為比表面積為400-650米2/克,孔體積為0.45-0.95毫升/克的無定形矽鋁。以無定形矽鋁為基準,其氧化矽的含量為10-80重量%,
優選為15-55重量%。
在另一個實施方案中,所述酸性矽鋁包括沸石。所述沸石可以是常作為裂解活性組份的沸石中的一種或幾種。所述沸石可以是具有大孔結構的沸石,如具有八面沸石、Beta沸石、Ω沸石結構的沸石;可以是具有中孔結構的沸石,如具有絲光沸石、ZSM-5沸石、ZSM-11沸石、ZSM-22沸石、ZSM-23沸石、ZSM-35沸石、ZSM-48沸石、ZSM-57沸石等結構的沸石;也可以是具有小孔結構的沸石,如具有Erionite沸石、ZSM-34沸石結構的沸石。優選具有八面沸石結構的沸石、具有Beta沸石結構的沸石、具有絲光沸石結構的沸石中的一種或幾種。本發明中,優選所述沸石為Y型分子篩。
所述的Y型分子篩選自HY(氫Y型分子篩)、REY(烯土Y型分子篩)、PY(含磷Y型分子篩)、USY(超穩Y型分子篩)、PUSY(含磷USY,包括PHY、REUSY(烯土超穩Y)),優選其中的USY、PUSY,進一步優選PUSY。所述分子篩可以是市售的商品,也可以採用任意的現有技術製備,例如,ZL00123139.1公開的製備USY的方法,Zl200410071122.6公開的製備PUSY的方法,這裏均作為參考引用。
所述成型按傳統方法進行,例如擠條成型。在擠出成型時可以加入適量助擠劑和/或黏合劑,然後擠出成型。所述助擠劑、膠溶劑的種類及用量為本領域技術人員所公知,在此不贅述。
所述乾燥和煅燒的方法為傳統方法,例如,採用
烘箱、網帶、轉爐加熱方法進行乾燥,乾燥條件包括溫度50-350℃,優選70-200℃,時間1-24小時,優選2-6小時;採用烘箱、網帶、轉爐加熱方法進行煅燒,煅燒條件包括溫度350-800℃,優選400-700℃,時間0.5-6小時,優選1-4小時。
本發明的發明人驚奇地發現,採用包括擬薄水鋁石組份與酸性矽鋁組份製備載體,由該載體製備氫化裂解催化劑時,催化劑具有更高的芳烴轉化性能。其中,所述擬薄水鋁石組份包括擬薄水鋁石PB1和擬薄水鋁石PB2或由其組成,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為0-60重量%;優選,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為5-60重量%;更優選,以乾基計並以載體為基準,PB1的含量為20-80重量%,PB2的含量為10-50重量%。所述載體各組份的總量為100重量%。
其中,以X光繞射表徵,所述PB1的κ1和κ2分別大於1至小於等於3,其中,κ1=h2/h1、κ2=h3/h2,h1、h2和h3分別為PB1的X光繞射譜圖中在2 θ角為24-30、35-41和46-52的三個繞射峰的峰高,和
其中,以紅外光譜表徵,PB2的δ值為1.5-4.5,其中,δ=I1/(I2+I3),I1為PB2的紅外羥基譜中3665-3680cm-1處吸收峰的峰高,I2為3720-3730cm-1處吸收峰的峰高,I3為3760-3780cm-1處吸收峰的峰高。
按照本發明的一個實施方案,進一步優選所述
PB1的κ1和κ2的值分別為1.02-2.3,更加優選所述PB1的κ1的值為1.2-2.3,κ2的值為1.02-1.4。
在足以滿足本發明要求的前提下,本發明對PB1的來源沒有特別限制,例如,可以是市售的商品或採用任意的現有方法製備。例如CN100999328B公開的一類採用硫酸鋁和偏鋁酸鈉中和法製備的擬薄水鋁石方法製備的擬薄水鋁石可滿足本發明的要求,這裏作為參考引用。
在一個實施方案中,製備本發明的PB1的方法包括以下步驟:1)在30-55℃下,使硫酸鋁與鹼性物質反應;2)調節pH到8.0-10.0;3)在30-60℃下恆溫乾燥;和4)過濾、水洗滌並乾燥步驟3)所得產物。
本發明中,所述PB1在κ1和κ2的值滿足要求的前提下,優選其中比表面積為100-350米2/克,孔體積為0.7-1.2毫升/克,進一步優選比表面積為150-280米2/克,孔體積為0.85-1.12毫升/克的擬薄水鋁石。
本發明中,所述擬薄水鋁石的孔體積、比表面積等,是將所述擬薄水鋁石於600℃煅燒4小時後,由BET氮吸附表徵得到。
PB2可以是將滿足前述要求的擬薄水鋁石PB1於70-400℃乾燥0.5-14小時,優選於220-330℃乾燥1-6小時後,得到PB1的改性物。採用紅外吸收光譜表徵,PB2的δ值為1.5-4.5,優選為1.8-3.8。
按照本發明提供的催化劑,所述選自VIII族和選自VIB族的金屬組份的含量為氫化裂解催化劑慣常含量,例如,以催化劑為基準並以氧化物計,所述催化劑含有1-10重量%的Ⅷ族金屬組份,5-40重量%的ⅥB族金屬組份;優選含有1.5-7重量%的Ⅷ族金屬組份,7-35重量%的ⅥB族金屬組份。所述VIB族金屬組份選自Cr、Mo或W中的一種或幾種,優選Mo和/或W,所述VIII族金屬組份選自Fe、Co或Ni中的一種或幾種,優選Co和/或Ni。
在足以將所述至少一種選自VIII族和至少一種選自VIB族的金屬組份負載於所述載體上的前提下,對具體負載方法沒有特別限制。優選的方法為浸漬法。分別或同時配製含選自VIII族和VIB族的金屬組份化合物的浸漬溶液。所述的浸漬根據浸漬液用量不同可以是過量液浸漬、孔飽和浸漬,根據浸漬實現的方式不同可以是浸泡法浸、噴淋浸漬等。通過對浸漬溶液的濃度、用量或載體用量的調節和控制,可以製備出指定金屬含量的所述催化劑,這是本領域技術人員所容易理解的,這裏不贅述。
按照本發明提供的催化劑製備方法,所述的第VIB族金屬化合物選自這些金屬的可溶性化合物中的一種或幾種,例如,可以是矽鎢酸、矽鎢酸鹽、磷鉬酸、磷鉬酸鹽、鉬酸鹽、仲鉬酸鹽、鎢酸鹽、偏鎢酸鹽、乙基偏鎢酸鹽中的一種或幾種。
所述的第VIII族金屬化合物選自這些金屬的鹽,包括它們的無機酸鹽或有機鹽。例如,所述無機鹽選自
硝酸鹽、碳酸鹽、鹼式碳酸鹽、次磷酸鹽、磷酸鹽、硫酸鹽、氯化物以及這些鹽類的部分分解產物中的一種或幾種,優選地,選自硝酸鹽、碳酸鹽或鹼式碳酸鹽中的一種或幾種。所述有機鹽為有機物與VIII族金屬結合生成的鹽類或可溶性錯合物。所述有機物可以是有機鹼、有機羧酸、胺類、酮類、醚類、烷基類,優選為有機羧酸鹽。
按照本發明提供的催化劑,還可以含有有機添加物。以所述催化劑為基準,並以碳元素計,所述有機添加物的含量不超過10重量%,進一步優選不超過6重量%。本發明的氫化裂解催化劑各組份的總量為100重量%。
所述的有機添加劑選自含氧和/或含氮的有機物中的一種或幾種。所述含氧化合物選自有機醇、有機酸中的一種或幾種。含氮有機化合物選自有機胺、有機銨鹽中的一種或幾種。具體地,選自含氧的有機物選自乙二醇、丙三醇、聚乙二醇(分子量為200~1500)、二乙二醇、丁二醇、乙酸、馬來酸、草酸、胺基三乙酸、1,2-環己烷二胺四乙酸、檸檬酸、酒石酸、蘋果酸中的一種或幾種,其中優選乙二醇、丙三醇、聚乙二醇和檸檬酸。含氮的有機物選自乙二胺、二亞乙基三胺、環己二胺四乙酸、胺基乙酸、次氮基三乙酸、EDTA及其銨鹽中的一種或幾種,其中優選EDTA和次氮基三乙酸。所述的有機添加劑也可以同時包括含有機醇和有機酸。
按照本發明提供的製備方法,當本發明的催化劑進一步含有有機化合物時,還包括引入有機化合物的步驟,所述有機化合物可以和第VIII族金屬一起引入,也可以在引
入第VIII族金屬之後引入,並進行乾燥。優選將有機物和第VIII族金屬配製成混合溶液通過浸漬的方式同時引入,之後進行乾燥。所述乾燥溫度和時間的選擇除了不足以使VIII族金屬鹽或錯合物分解外,還應允許在催化劑中保留大部分所引入的有機物,例如保留50%以上的有機物,更優選地,保留70%以上的有機物。其方法可以是現有技術中任意一種可實現上述目的的方法。例如,加熱乾燥,減壓乾燥以及加熱結合減壓乾燥等方法。當所述乾燥方法為加熱乾燥時,優選的乾燥溫度不超過250℃,進一步優選不超過200℃,更加優選不超過180℃。例如,在一個優選的實施方式中,所述乾燥溫度為70℃~180℃。
按照本發明,在製備含有有機化合物的所述催化劑時,以碳元素計並以所述催化劑為基準,優選通過選擇所述有機化合物的引入量使得最終催化劑中,所述有機添加物的含量不超過10重量%,進一步優選不超過6重量%。
按照本領域中的傳統方法,所述氫化處理催化劑在使用之前,通常可在氫氣存在下,於140-370℃的溫度下用硫、硫化氫或含硫原料進行預硫化。這種預硫化可在器外進行也可在器內原位硫化。這種預硫化將所述氫化處理催化劑所負載的金屬組份轉化為金屬硫化物組份。
本發明提供的催化劑可用於各類烴油原料的氫化裂解或氫化改質。用於氫化裂解或氫化改質的反應條件為慣常的氫化裂解或氫化改質反應條件,例如反應溫為度200-420℃、進一步優選為220-400℃,壓力為2-18兆帕、進
一步優選為2-15兆帕,液時空速為0.3-10小時-1、進一步優選為0.3-5小時-1,氫油體積比為50-5000、進一步優選為50-4000。
所述氫化裂解或氫化改質的反應的裝置可以在任何足以使所述原料油在氫化處理反應條件下與所述催化劑接觸反應的反應裝器中進行,例如,在所述固定床反應器,移動床反應器或沸騰床反應器中進行。
與現有技術提供催化劑相比,本發明提供催化劑具有更好的氫化脫芳烴性能。例如,採用本發明提供的催化劑在6.4MPa中壓條件下加工催化裂解尾油,尾油芳烴含量相對降低可達10-30%。
附圖用以對本發明的進一步理解,並且構成說明書的一部分,與下面的具體實施方式一起用於說明本發明,但並不構成對本發明的限制。在附圖中:
圖1是擬薄水鋁石的XRD譜圖,其中PB1-1是滿足本發明要求的擬薄水鋁石;PB2-2為PB1-1的一種改性物;SB(Sasol公司生產的擬薄水鋁石,商品名為SB粉)是一種不能滿足本發明要求的擬薄水鋁石。
圖2是擬薄水鋁石的IR-OH譜圖,其中PB2-1為一種PB1-1的改性物;PB2-2為另一種PB1-1的改性物;PB2-3為PB1-1於600℃煅燒的產物。
以下通過實施例對本發明作進一步說明。
實驗中,XRD在德國西門子公司的D5005型X射線繞射儀上進行,Cu靶,Ka輻射,固體探測器,40kV,40mA,步進掃描,步幅0.02°,掃描範圍5~70°。
IR-OH譜圖在美國BIO-RAD公司FT3000型傅立葉變換紅外光譜儀進行測定,15mm的自支撐片,並真空至10-3Pa,保持1h,冷至室溫後掃描1000~4000cm-1波數範圍。
實施例及對照例中所使用的擬薄水鋁石、製備方法或來源:
PB1-1
將澄清透明的500mL濃度為93g/L的硫酸鋁和濃度為195g/L的偏鋁酸鈉(苛性係數為1.6)同時緩慢加入2L帶攪拌的反應釜中,控制反應溫度為40℃,pH值7.3。反應完全後,攪拌加入濃度為0.5mol/L的碳酸鈉至溶液pH值為9.7。恆溫50℃反應1小時後,過濾,去離子水洗滌三次,烘箱中通風120℃溫度乾燥3hr,得到擬薄水鋁石PB1-1。PB1-1的h1,h2,h3,k1,k2以及其孔體積列於表1。
PB1-2
將澄清透明的600mL濃度為48g/L的硫酸鋁和濃度8%的氨水同時緩慢加入2L帶攪拌的反應釜中,反應過濾,再加入氨水控制反應溫度為35℃,pH值6.0。反應完全後,過濾,將濾餅打漿,攪拌加入碳酸氫銨至溶液pH值為9.5。
恆溫35℃反應12小時後,過濾,去離子水洗滌三次,烘箱中通風120℃溫度乾燥3hr,得到擬薄水鋁石PB1-2。PB1-2的h1,h2,h3,k1,k2以及其孔體積列於表1。
PB1-3
將澄清透明的600mL濃度為93g/L的硫酸鋁和濃度8%的氨水同時緩慢加入2L帶攪拌的反應釜中,控制反應溫度為50℃,pH值4.6。反應完全後,過濾,將濾餅打漿,攪拌加入碳酸鈉至溶液pH值為8.4。恆溫35℃反應0.5小時後,過濾,去離子水洗滌三次,烘箱中通風120℃溫度乾燥3hr,得到擬薄水鋁石PB1-3。PB1-3的h1,h2,h3,k1,k2以及其孔體積列於表1。
SB
Sasol公司生產的擬薄水鋁石,商品名為SB粉。SB的h1,h2,h3,k1,k2以及其孔體積列於表1。
其中,SB不能滿足本發明要求。
實施例及對照例中所使用的擬薄水鋁石改性物及其製備方法:
PB2-1
將300克PB1-1置於馬弗爐中,加熱至250℃並在該溫度下恆溫3小時,得到PB2-1。PB2-1的I1,I2,I3和δ值列於表2。
PB2-2
將300克PB1-1置於馬弗爐中,加熱至300℃並在該溫度下恆溫3小時,得到PB2-2。PB2-2的I1,I2,I3和δ值列於表2。
PB2-3
將300克PB1-1置於馬弗爐中,加熱至600℃並在該溫度下恆溫3小時,得到PB2-3。PB2-3的I1,I2,I3和δ值列於表2。
PB2-4
將300克PB1-2置於馬弗爐中,加熱至230℃並在該溫度下恆溫5小時,得到PB2-4。PB2-4的I1,I2,I3和δ值列於表2。
PB2-5
將300克PB1-3置於馬弗爐中,加熱至330℃並在該溫度下恆溫2小時,得到PB2-5。PB2-5的I1,I2,I3和δ值列於表2。
對照例1
將298克擬薄水鋁石SB(乾基0.75,乾基測定方法為將一定量的原粉置入帶蓋坩堝放入馬弗爐中,升溫至700℃恆溫1hr後,計算剩餘物同原粉的比值,下同)與366.7克超穩分子篩LAY(中石化催化劑分公司長嶺催化劑廠生產,單元胞穴尺寸24.58埃,孔體積0.39ml/g,乾基0.75)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾3小時,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表3。
降溫至室溫後,取100克載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)50克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸68ml水溶液浸漬,180℃烘10小時,得到催化劑R-1。以催化劑總量為基準,R1中金屬組份的質量份數(為計算值,下同)列於表3。
實例1
將300克擬薄水鋁石粉PB1-1(乾基0.75)同366.7克超穩分子篩LAY、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾3小時,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表3。
降溫至室溫後,取100克載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸77ml水溶液浸漬,180℃烘10小時,得到催化劑C-1。以催化劑總量為基準,C-1中金屬組份的質量份數列於表3。
實例2
將133克擬薄水鋁石粉PB1-1同136克乾基含量0.92的PB2-2,366.7g超穩分子篩LAY、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表3。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸84ml水溶液浸漬,180℃烘10小時,得到催化劑C-2。以催化劑總量為基準,C-2中金屬組份的質量份數列於表3。
對照例2
同實例2,所不同的是用125g PB2-3代替PB-2-2,得到催化劑R-2。以催化劑總量為基準,R-2中金屬組份的質量份數列於表3。
實例3
將267g克擬薄水鋁石粉PB1-3(乾基0.76)同28g乾基含量0.89的PB2-1,340g含磷超穩分子篩PUSY(中石化催化劑分公司長嶺催化劑廠生產,商品名USY-5,五氧化二磷含量1.2%,單元胞穴尺寸24.44埃,孔體積0.40ml/g,乾基0.81,)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表3。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸90ml水溶液浸漬,140℃烘3小時,得到催化劑C-3。以催化劑總量為基準,C-3中金屬組份的質量份數列於表3。
實例4
將530g克擬薄水鋁石粉PB1-3(乾基0.76)同56g乾基含量0.89的PB2-1,62g含磷超穩分子篩PUSY(中石化催化劑分公司長嶺催化劑廠生產,商品名USY-5,五氧
化二磷含量1.2%,單元胞穴尺寸24.44埃,孔體積0.40ml/g,乾基0.81,)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,480℃溫度下煅燒8小時,得載體,催化劑載體組成見表3。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)30克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)18克、25g檸檬酸90ml水溶液浸漬,110℃烘20小時,得到催化劑C-4。以催化劑總量為基準,C-4中金屬組份的質量份數列於表3。
實例5
本實例說明本發明提供催化劑的性能。
所用原料油為沙輕減二減壓瓦斯油,其物化性質見表4。
本實例中,催化劑的評價方法是:將催化劑破碎成直徑2-3毫米的顆粒,在30毫升固定床反應器中裝入催化劑20毫升,反應前先在氫氣氛下用含2重%二硫化碳的煤油按照如下程式進行硫化,然後切換反應原料反應。
硫化程式:升溫至150℃,引入硫化油,恆溫1hr待吸附溫波通過反應器,以60℃/hr升溫至230℃,穩定2hr,以60℃/hr升溫至360℃,穩定6hr。
置換反應油,調整反應溫度至355℃,至少穩定20hr。反應氫分壓為6.4兆帕,液時空速(LHSV)1小時-1,氫油比(體積)800,評價的催化劑及其結果列於表5中。
反應後將所得產品通過350℃進行減壓蒸餾,所得產品進行質譜族組成分析,結果見表5所示。
由於催化劑評價反應壓力較低,使得尾油芳烴接近所謂的熱力學平衡區域,採用本方法後尾油芳烴含量相對降低10-35%。
對照例3
將267克擬薄水鋁石SB(乾基0.75,乾基測定方法為將一定量的原粉置入帶蓋坩堝放入馬弗爐中,升溫至700℃恆溫1hr後,計算剩餘物同原粉的比值,下同)與395克無定形矽鋁(德國Condea公司生產,商品名Sira-40,孔體積0.88ml/g,比表面468m2/g,二氧化矽重量含量40%,乾基0.76)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾3小時,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表6。
降溫至室溫後,取100克載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)50克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸78ml水溶液浸漬,180℃烘10小時,得到催化劑R-3。以催化劑總量為基準,R3中金屬組份的質量份數(為計算值,下同)列於表6。
實例6
將267克擬薄水鋁石粉PB1-1(乾基0.75)同3695克無定形矽鋁(同對照例3)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾3小時,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表6。
降溫至室溫後,取100克載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸87ml水溶液浸漬,180℃烘10小時,得到催化劑C-5。以催化劑總量為基準,C-5中金屬組份的質量份數列於表6。
實例7
將133克擬薄水鋁石粉PB1-1同109克PB2-2(乾基0.92),394g無定形矽鋁(同實例6)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表6。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸94ml水溶液浸漬,180℃烘10小時,得到催化劑C-6。以催化劑總量為基準,C-6中金屬組份的質量份數列於表6。
對照例4
同實例7,所不同的是用100g PB2-3代替PB-2-2,得到催化劑R-4。以催化劑總量為基準,R-4中金屬組份的質量份數列於表6。
實例8
將131.6g克擬薄水鋁石粉PB1-3(乾基0.76)同224.7g PB2-1(乾基0.89),267g無定形矽鋁(德國Condea公司生產,商品名Sira-20,孔體積0.49ml/g,比表面590m2/g,二氧化矽重量含量20%,乾基0.75)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,600℃溫度下煅燒3小時,得載體,催化劑載體組成見表6。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)51克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)8.7克、10.5g檸檬酸92ml水溶液浸漬,140℃烘3小時,得到催化劑C-7。以催化劑總量為基準,C-7中金屬組份的質量
份數列於表6。
實例9
將460g克擬薄水鋁石粉PB1-3(乾基0.76)同56g PB2-1(乾基0.89),267g無定形矽鋁(德國Condea公司生產,商品名Sira-30,孔體積0.78ml/g,比表面455m2/g,二氧化矽重量含量30%,乾基0.75)、田菁粉16克混合,擠成外接圓直徑為1.6毫米的三葉形條,120℃烘乾,480℃溫度下煅燒8小時,得載體,催化劑載體組成見表6。
降溫至室溫後,取100g載體用含偏鎢酸銨(四川自貢硬質合金廠,氧化鎢含量為82重量%)30克、鹼式碳酸鎳(江蘇宜興徐遲化工有限公司,氧化鎳含量為51重量%)18克、25g檸檬酸94ml水溶液浸漬,110℃烘20小時,得到催化劑C-8。以催化劑總量為基準,C-8中金屬組份的質量份數列於表6。
實例10
以催化劑R-3、C-5、C-6和R-4重複實例5,結果見表7所示:
由於催化劑評價反應壓力較低,使得尾油芳烴接近所謂的熱力學平衡區域,採用本方法後尾油芳烴含量相對降低10-55%。
Claims (15)
- 一種氫化裂解催化劑,含有載體和至少一種選自Ⅷ族和至少一種選自VIB族的金屬組份,所述載體含有酸性矽鋁組份和源自於擬薄水鋁石組份的氧化鋁,以載體為基準,酸性矽鋁組份的含量為3-80重量%,源自於擬薄水鋁石組份的氧化鋁的含量為20-95重量%,其特徵在於,所述載體由酸性矽鋁組份與擬薄水鋁石組份混合、成型、乾燥並煅燒得到,所述擬薄水鋁石組份包括擬薄水鋁石PB1和擬薄水鋁石PB2,以乾基計並以載體為基準,PB1的含量為10-90重量%,PB2的含量為0-60重量%,以X光繞射表徵,所述PB1的κ1和κ2分別大於1至小於等於3,其中,κ1=h2/h1、κ2=h3/h2,h1、h2和h3分別為PB1的X光繞射譜圖中在2 θ角為24-30°、35-41°和46-52°的三個繞射峰的峰高,以紅外光譜表徵,PB2的δ值為1.5-4.5,其中,δ=I1/(I2+I3),I1為PB2的紅外羥基譜中3665-3680cm-1處吸收峰的峰高,I2為3720-3730cm-1處吸收峰的峰高,I3為3760-3780cm-1處吸收峰的峰高。
- 如請求項1所述的催化劑,其中,以載體為基準,酸性矽鋁組份的含量為5-65重量%,源自於擬薄水鋁石組份的氧化鋁的含量為30-90重量%。
- 如請求項2所述的催化劑,其中,以X光繞射表徵,所述PB1的κ1和κ2分別為1.02-2.4。
- 如請求項1所述的催化劑,其中所述PB1的比表面積為100-350米2/克,孔體積為0.7-1.2毫升/克。
- 如請求項1所述的催化劑,其中所述酸性矽鋁包括沸石和/或無定形矽鋁。
- 如請求項1所述的催化劑,其中所述酸性矽鋁為選自HY沸石、稀土型Y沸石、稀土型HY沸石、超穩Y沸石、稀土型超穩Y沸石、脫鋁Y型沸石中的一種或幾種Y型分子篩。
- 如請求項6所述的催化劑,其中所述Y型分子篩的單元胞穴尺寸為2.460-2.430nm,比表面積為550-700米2/克,孔體積為0.30-0.45毫升/克。
- 如請求項6所述的催化劑,其中所述Y型分子篩含有磷,以所述分子篩為基準,磷的含量為0.1-2.5重量%。
- 如請求項5所述的催化劑,其中,以所述無定形矽鋁為基準,其氧化矽的含量為10-80重量%。
- 如請求項5所述的催化劑,其中所述無定形矽鋁的比表面積為350-750米2/克,孔體積為0.4-1.2毫升/克。
- 如請求項1所述的催化劑,其中所述Ⅷ族的金屬組 份選自鎳和/或鈷,所述VIB族的金屬組份選自鉬/或鎢,以氧化物計並以所述催化劑為基準,所述鎳和/或鈷的含量為1-15重量%,所述鉬/或鎢的含量為5-40重量%。
- 如請求項2所述的催化劑,其中以乾基計並以載體為基準,PB1的含量為20-80重量%,PB2的含量為10-50重量%。
- 如請求項1所述的催化劑,其中所述PB2的δ值為1.8-3.8。
- 如請求項1所述的催化劑,其中所述PB2為PB1於70-400℃乾燥0.5-14小時的改性物。
- 一種如請求項1所述的催化劑在烴油加工中的用途。
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CN106554815B (zh) * | 2015-09-30 | 2019-11-15 | 中国石油化工股份有限公司 | 一种由高硫氮劣质柴油生产清洁柴油的方法 |
US11951463B2 (en) * | 2017-03-29 | 2024-04-09 | ExxonMobil Engineering & Technology Company | Catalyst compositions and their use in aromatic alkylation processes |
CN108714434B (zh) * | 2018-06-04 | 2021-09-07 | 中国中化股份有限公司 | 一种轻油型加氢裂化催化剂及其制备方法 |
CN114522694B (zh) * | 2020-10-27 | 2023-07-14 | 中国石油化工股份有限公司 | 一种加氢脱硫催化剂及其制备方法和应用 |
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CN113562751B (zh) * | 2020-04-28 | 2023-05-09 | 中国石油化工股份有限公司 | 改性拟薄水铝石及其制备方法和改性氧化铝及加氢催化剂 |
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