CN114433211B - 化工型加氢裂化催化剂及其制法和应用 - Google Patents
化工型加氢裂化催化剂及其制法和应用 Download PDFInfo
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- CN114433211B CN114433211B CN202011115942.6A CN202011115942A CN114433211B CN 114433211 B CN114433211 B CN 114433211B CN 202011115942 A CN202011115942 A CN 202011115942A CN 114433211 B CN114433211 B CN 114433211B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 154
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 77
- 239000000126 substance Substances 0.000 title abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 149
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 142
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 40
- 239000003921 oil Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012018 catalyst precursor Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- -1 VIB metal oxide Chemical class 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 6
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 18
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 12
- 238000004898 kneading Methods 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 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 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- 101000804764 Homo sapiens Lymphotactin Proteins 0.000 description 2
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 229910021627 Tin(IV) chloride Inorganic materials 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
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
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- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- FPJNQJHCHVUNTK-UHFFFAOYSA-N platinum;dihydrate Chemical compound O.O.[Pt] FPJNQJHCHVUNTK-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
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- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
本发明涉及一种化工型加氢裂化催化剂及其制法和应用。本发明所述化工型加氢裂化催化剂,包括以下组分:a)β沸石;b)层状MWW型沸石,薄片厚度范围为2‑12nm;c)金属功能组分;d)粘结剂,以及任选的e)金属功能调节组分。该催化剂可用于富含稠环芳烃原料油的加氢裂化反应中,生产轻质芳烃和轻质裂解料,具有原料单程转化率高、化工料收率高、催化剂稳定性好的特点。
Description
技术领域
本发明涉及炼化加氢裂化领域的催化剂技术,进一步地涉及一种化工型加氢裂化催化剂及其制法和应用。
背景技术
加氢裂化是重质馏分油深度加工的主要工艺之一,是指通过加氢反应使原料油中的10%以上的分子变小的加氢工艺。加氢裂化技术是原油二次加工、重油轻质化的重要手段之一,由于它对原料的适应性强、操作和产品方案都十分灵活以及产品质量好等特点,已成为生产优质轻质油品及解决化工原料来源的重要途径。在现有工艺中,轻油型加氢裂化工艺以汽油或石脑油为目标产品。通过石脑油催化重整过程生产轻质芳烃,也可通过石脑油蒸汽裂解过程生产烯烃产品。
随着柴油需求增长停滞,国VI标准在2019年实施,炼化企业出现了巨量的劣质油品过剩的情况,如催化柴油和乙烯焦油。催化柴油是催化裂化过程的主要产物之一,全国年产量约5000万吨。虽然它们的沸点在柴油馏分,但由于含有大量稠环芳烃等原因,将其加工成柴油的经济性不佳,部分企业只能将其作为燃料油使用。
在已有炼油型加氢裂化催化剂和工艺技术的基础上,相关研究机构开发了可将催化柴油转化为高辛烷值汽油调和组分的技术,如中国专利CN101724454A和CN102839018A公开的技术。其所得重石脑油馏分的芳烃含量介于50-65%之间,可用作高辛烷值汽油调和组分,所采用的催化剂含有20-75wt%的Y型沸石。但由于Y型沸石的孔道开阔,不具备裂解非芳烃的择形效应,所得产物C8、C9和C10馏分的芳烃含量偏低,非芳烃含量偏高,因无法达到重整生成油的指标,其进入芳烃联合装置作为生产苯和对二甲苯的原料存在明显的困难。中国专利CN1955262A公开了一种两段加氢裂化方法,其加氢裂化催化剂含Pt-Pd贵金属及非贵金属、高孔道空间指数的Y沸石和氧化铝,原料是催化柴油。其石脑油产品的芳潜值最高只有76.8%,芳烃的纯度不高,也达不到芳烃联合装置的要求。
研究发现,加氢裂化催化剂中作为酸性基质的沸石的空间指数对不同类型烃类分子的转化路径选择性具有决定性作用。孔道空间指数(spaciousness index,SI)是表征不同十二元环沸石孔道的开阔程度的指标,介于3~21之间。Y型沸石的空间指数接近20(见文献Catalytic hydrocracking—mechanisms and versatility of the process,ChemCatChem 2012,4,292–306)。相比于孔道空间指数较高的USY沸石,孔道空间指数介于6~18的低空间指数沸石具有开环和选择裂化能力强、氢转移效应弱的优点。其中,具有三维十二元环孔道结构、孔道空间指数介于15~18的β沸石的孔道尺寸小于USY沸石,且不存在超笼,其孔道特点赋予了其优良的异构和裂解能力,在加氢裂化反应上获得了应用。
中国专利CN103100429A公开了一种柴油加氢改质催化剂载体及其制备方法,其中的β沸石经过水热处理均匀脱铝,使其对长链烷烃和环烷烃具有很好的异构和裂解作用,能够在保持高柴油收率的同时,较大幅度降低柴油馏分的凝点,提高改质柴油的十六烷值,其目标产品不是芳烃等化工产品,可归为中油型加氢裂化催化剂的范畴。专利CN105435836A公开了一种加氢裂化催化剂及其制备和应用,采用ZSM-5和Moβ沸石的混合物作为酸功能组分,所负载的活性金属组分还需要经过硫化过程转化为金属硫化物组分,其对双环及以上多环芳烃的加氢裂化反应和理想产物的选择性等明显提高,具有较高的四氢萘转化率和BTX选择性。
但是β沸石十二元环孔道的直径约0.67nm,原料或反应过程中产生的三环以上稠环芳烃分子无法进入孔道并与活性中心接触,这导致对重稠环芳烃转化能力不佳。
因此,亟需开发化工型加氢裂化催化剂,解决催化剂对重稠环芳烃转化能力不佳等问题,将这些劣质油品最大化转化为满足芳烃联合装置质量指标的轻质芳烃,并副产可作为烯烃原料的优质轻烃,直接为芳烃、烯烃等化工装置提供原料,通过炼化一体化实现劣质重芳烃资源的利用及芳烃产业的降本增效。
发明内容
本发明所要解决的技术问题是现有技术中的加氢裂化催化剂对芳烃和轻烃化工料选择性低、对重稠环芳烃转化能力不佳的问题。本发明提供的化工型加氢裂化催化剂用于富含稠环芳烃原料油的加氢裂化反应中,具有芳烃和轻烃裂解料选择性高、对重稠环芳烃转化能力强等特点,可实现催化柴油等劣质富芳油品的化工利用。
本发明的一个目的是提供一种化工型加氢裂化催化剂。
本发明所述加氢裂化催化剂,包括以下组分:
a)β沸石;
b)层状MWW型沸石,薄片厚度2-12nm;
c)金属功能组分;
d)粘结剂;
任选地,还包括e)金属功能调节组分。
以上所述本发明的加氢裂化催化剂,以总沸石重量为100份计,所述的金属功能组分以元素为基础计为以元素为基础计为0.1~60份,优选0.2~50份,更优选0.2~45份;所述粘结剂为5~2000份,优选10~1000份,更优选为10~900份。
以上所述本发明的加氢裂化催化剂,其中β沸石占总沸石量的50-99%wt,优选占60-95%wt。所述的总沸石包括以上所述的β沸石和层状MWW型沸石。占总重优势的β沸石发挥主导性裂解作用,薄片层状MWW结构沸石则可实现对重稠环芳烃大分子的转化。
以上所述本发明的加氢裂化催化剂中含有的β沸石,对加氢精制原料油的烷烃和四氢萘系烃类具有很强的异构和裂解能力,单程转化率高。而且,其孔道空间指数介于15~18,孔道择形效应能使轻质芳烃馏分内的烷烃、环烷烃进一步裂解,轻质芳烃选择性高;同时因β-scission和脱烷基反应的发生而大量副产C2-C5轻烃。
以上所述β沸石的优选硅铝比介于10~200,更优选硅铝比介于30-100的β沸石。此间的β沸石不仅具有强的裂解能力,还具有强的抗氮能力,这对催化剂的长周期稳定运行非常重要。
以上所述本发明的加氢裂化催化剂中含有的层状MWW型沸石为薄片层状的沸石,其薄片厚度范围为2-12nm,优选为2-10nm,更优选为2-6nm。以上所述本发明的加氢裂化催化剂中含有的层状MWW型沸石的硅铝比介于10~100。
MWW型沸石为层状结构,层间以氧桥键相连,包括尺寸为0.4nm×0.59nm的层内十元环二维孔道和尺寸为0.71nm×0.71nm×1.82nm的十二元环超笼,其表面分布着含丰富活性中心的0.71nm×0.71nm×0.71nm的杯状结构。经发明人研究发现,典型MWW型沸石,例如MCM-22沸石,与β沸石组合的催化剂无法达到所期望的技术效果。典型MWW型沸石,其单层与单层之间为化学键缩合在一起,无法轻易打开,最终形成的沸石颗粒可分散开的厚度通常较大(大于12nm),存在活性中心的空穴不处于开放状态,重稠环芳烃大分子不能接近。但是如果将层状MWW型沸石的薄片厚度范围控制在2-12nm,优选2-10nm,更优选2~6nm,形成拟二维结构材料,十二元环超笼打开,形成以杯状结构中活性中心为主体的薄片层状MWW型沸石,对重稠环芳烃大分子的可接近性好,可实现其有效转化。由此本发明的薄片层状的MWW型沸石与β沸石协同作用才能实现很好的芳烃和轻烃化工料选择性高且对重稠环芳烃转化能力优异的技术效果。
MWW型沸石的分层,可以通过现有技术的分层方法,如A.Corma等报道(Nature,1998,393:353-356),从MWW结构二维层状前驱体出发通过表面活性剂溶胀-超声剥离制得的ITQ-2沸石,具有典型的薄层状结构。二维层状(即薄片层状)MWW型沸石还可通过直接合成方法得到,采用有机硅烷化试剂强制层分离和双有机模板剂直接水热合成法分别得到了二维纳米片材料SRZ-21沸石(见中国专利CN101121523A和CN101121524A)和SCM-1沸石(见中国专利CN2014000867,WO2015/042114A1)。本发明所述层状MWW型沸石进一步优选薄片厚度为2~10nm的ITQ-2沸石、SRZ-21沸石和SCM-1沸石。有关本发明优选的层状MWW型沸石及其制备方法,可由中国专利CN101121523A和CN101121524A(同族US 8030508B2)及WO2015/042114A1全文引入。
根据本发明的一个方面:本发明所述的催化剂,其中所述金属功能组分为贵金属铂Pt和/或钯Pd;或者,为非硫化态的VIII族金属、非硫化态的IIB族金属中的至少一种与非硫化态的VIB族金属氧化物的组合物。
以重量份数计,在本发明所述催化剂组合物中所述金属功能组分以元素为基础计算,以总沸石重量为100份计,所述的金属功能组分以元素为基础计为0.1~60份,优选0.2~50份,更优选0.2~45份。具体例如0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、54、55、56、57、58、59、60份等。
具体地,
根据本发明的一个优选方案,所述催化剂组合物中金属功能组分为非硫化态的VIII族金属-IIB族金属-VIB族金属氧化物的复合物(组合物),即为非硫化态的VIII族金属和/或IIB族金属的至少一种与VIB族金属氧化物的至少一种的复合(组合)。经发明人研究发现,VIII族金属和/或IIB族金属的至少一种与VIB族金属氧化物在氢气气氛中还原后,具有适中的加氢能力,抗硫性好,特别适用于化工型加氢裂化催化剂中。
以上所述的金属功能组分,更优选为非硫化态的镍Ni、钴Co、锌Zn中的至少一种、与氧化钼MoOx和/或氧化钨WOx的复合物。其中x代表氧空穴的存在,x值介于2-2.6,可理解为四价VIB族金属氧化物和六价VIB族金属氧化物的复合物。
其中所述IIB族金属优选为锌。该组分可以作为化合物,例如氧化物或锌离子,与最终催化剂组合物中的一种或多种其它成分化学结合,或者作为金属元素存在于该组合物中。可以使用的典型含锌化合物是硝酸锌、氯化锌、草酸锌、乙酸锌,特别优选硝酸锌作为锌组分的来源。
其中所述VIII族金属优选选自由钴、镍组成的组中的至少一种。该组分可以作为化合物,例如氧化物,与最终催化剂组合物中的一种或多种其它成分化学结合,或者作为金属元素存在于该组合物中。可以使用的典型钴族化合物是硝酸钴、氯化钴、草酸钴,优选硝酸钴作为特别优选的钴组分的来源。可以使用的典型镍族化合物是硝酸镍、硫酸镍、卤化镍、草酸镍、乙酸镍,优选硝酸镍作为特别优选的镍组分的来源。
所述VIB族金属氧化物优选选自由氧化钼和氧化钨组成的组中的至少一种。VIB族金属氧化物可以以任何合适的方式结合到催化剂内,例如与催化剂载体共沉淀、共胶凝、混捏、离子交换或浸渍,优选使用所述金属的水溶性化合物浸渍,烘干后焙烧,金属为氧化态。所述氧化钼为二氧化钼和/或三氧化钼,可以使用的典型钼族化合物是钼酸铵、三氧化钼,优选钼酸铵作为氧化钼的来源。所述氧化钨为二氧化钨和/或三氧化钨,可以使用的典型钨族化合物是钨酸铵、钨酸钠,优选钨酸铵作为氧化钨的来源。
所述金属功能组分为VIII族金属-IIB族金属-VIB族金属氧化物复合时,以金属元素为基础计,其中VIB族金属与VIII族金属和IIB族金属之和的重量比比为(0.2~20):1,优选(0.3~15):1,更优选(1~10):1。在还原过程中形成氧空位,通过XPS(X光电子能谱)方法可确定非硫化态的镍Ni和/或钴Co、非硫化态的Zn、氧化钼MoOx和/或氧化钨WOx的复合物中的x值。
根据本发明的一个优选方案,所述催化剂组合物中金属功能组分为贵金属铂、钯中的至少一种。
所述Pt和/或Pd贵金属为加氢催化剂中常见的金属功能组分;Pt、Pd贵金属可以以任何合适的方式结合到催化剂内,例如与催化剂载体共沉淀、共胶凝、离子交换或浸渍,优选使用所述金属的水溶性化合物浸渍。可以使用的典型铂族化合物是氯铂酸、氯铂酸铵、溴铂酸、二氯化铂、四氯化铂水合物、氯化四胺合铂、硝酸四胺合铂、二氯羰基二氯化铂、二硝基二氨基合铂、氯化铂、二水合氯化铂、硝酸铂,优选氯化四胺合铂作为特别优选的铂组分的来源。可以使用的典型钯族化合物是氯化钯、二水合氯化钯、硝酸钯二水合物、氯化四氨合钯,优选氯化四氨合钯作为特别优选的钯组分的来源。
根据本发明的一个方面:本发明所述的催化剂,其中还可含有金属功能调节组分,优选包括锡Sn和/或铋Bi。金属功能调节组分可以影响复合金属氧化物加氢相的电子云结构,在一定范围内增强或减弱加氢功能,起到调节金属功能的作用。以金属元素为基础计,金属功能组分与金属功能调节组分的重量比为(0.1~20):1,优选为(0.1~15):1。
根据本发明的一个方面:本发明所述的催化剂,其中所述粘结剂可选自本领域现有技术中常用的催化剂粘结剂,以提供良好的机械性质和织构性质。本发明的粘结剂优选包括氧化铝、氧化硅中的一种,所述氧化铝具体可以为拟薄水铝石等,所述氧化硅具体可以为多孔硅胶粉、氨型硅溶胶的组合物等。
以上所述粘结剂以重量份数计,在本发明所述催化剂组合物中,以总沸石重量为100份计,所述粘结剂为5~2000份,优选10~1000份,更优选10~900份,具体例如10、20、30、40、50、60、70、80、80、100、200、300、400、500、600、700、800、900份等。
本发明所述粘结剂可以以任何合适的方式结合到催化剂内,例如与沸石混捏、挤条、养生、烘干和焙烧后就可得到催化剂载体。
根据本发明的催化剂体系,本发明所述催化剂中还可包括本领域催化剂的常规组分,例如硅藻土、活性粘土等。用量可为通常用量。
本发明的另一个目的是提供本发明所述加氢裂化催化剂的制备方法。
本发明所述的加氢裂化催化剂可采用本领域催化剂制备的任何方法进行制备,没有特别的限定。例如本发明所述催化剂的制备可以包括将包含所述沸石的催化剂载体成型并负载包括所述金属功能组分在内的组分之后焙烧活化后得到催化剂前体,之后将催化剂前体还原的步骤。其中所述载体成型可通过将所述沸石与所述粘结剂等一起采用本领域通常的挤条、滚球或油柱成型等方法进行;所述负载金属可通过本领域通常的将金属与催化剂载体共沉淀、共胶凝、混捏、离子交换或浸渍等方法进行。
以上所述本发明复合催化剂体系的制备方法,优选地可以包括以下步骤:
1)将包括所述β沸石和层状MWW型沸石与所述粘合剂在内的组分混合干燥后在500~600℃空气气氛中焙烧得所需的催化剂载体;
2)以包括所述贵金属铂和/或钯的金属化合物,或者包括所述VIII族金属化合物及IIB族金属化合物的至少一种和VIB族金属化合物在内的金属组分,配制金属水溶液;通过等体积浸渍方法浸渍以上所得催化剂载体,干燥后在450~580℃空气气氛中焙烧得到催化剂前体;
3)将所得催化剂前体在氢气条件下还原到400~500℃,得到所述催化剂;
任选地,在上述步骤2)之前,将所述金属功能调节组分的金属化合物配制成金属水溶液,等体积浸渍步骤1)所得催化剂载体,干燥后在350~500℃空气气氛中焙烧。
以上所述本发明复合催化剂体系的制备方法,更具体地可以包括:将所述沸石(包括所述β沸石和层状MWW型沸石)与所述粘结剂混合后,混捏、挤条、60~150℃烘干后在500~600℃空气气氛中焙烧3~6小时,即得所需的催化剂载体。任选地,将所述金属功能调节组分配制成水溶液,等体积浸渍所得催化剂载体,之后60~150℃烘干后在350~500℃空气气氛中焙烧1~6小时后备用。以Pt和/或Pd金属化合物,或者以VIII族金属化合物和IIB族金属化合物中的至少一种和VIB族金属化合物配制金属功能组分水溶液,通过等体积浸渍方法处理上述任选地负载金属功能调节组分的催化剂载体,之后60~150℃烘干后在450~580℃空气气氛中焙烧1~6小时,得到催化剂前体。将催化剂前体在氢气条件下还原到400~500℃并保持2~24小时,即可完成催化剂活化程序,得到所述催化剂。
本发明的再一个目的是提供本发明所述化工型加氢裂化催化剂在加氢裂化反应中的应用。
本发明所述化工型催化剂在加氢裂化反应中的应用包括将本发明所述化工型催化剂在加氢裂化反应条件下与原料油接触的步骤。
根据本发明的一个方面:本发明所述催化剂在加氢裂化反应中适用的原料油为富含芳烃的原料油,具体可为经过加氢精制处理的催化柴油、乙烯焦油等。所述原料油中芳烃含量大于等于50重量%,例如50%、55%、60%、65%、70%、75%、80%、85%、90%、95%、100%。进一步优选所述原料油氮含量≤20ppm、硫含量≤200ppm。
通常加氢裂化原料油经过通常的加氢精制处理后,其氮含量低于20ppm,在高沸点范围内以多烷基咔唑的形式存在,例如20、19、18、17、16、15、14、13、12、11、10、9、8、7、6、5、4、3、2、1ppm等;可以优选适用于本发明所述的催化剂的加氢裂化反应中。
通常加氢裂化原料油经过通常的加氢精制处理后,其硫含量低于200ppm,在高沸点范围内以多烷基二苯并噻吩的形式存在,例如200、190、180、170、160、150、140、130、120、110、100、90、80、70、60、50、40、30、20、10ppm等;在优选的条件下,其硫含量低于100ppm。
本发明的加氢催化剂,无论是负载在β沸石和薄片层状MWW型沸石的复合载体上的VIII族金属-IIB族金属-VIB族金属氧化物复合物,还是Pt、Pd贵金属中的至少一种,均具有良好的抗硫能力,能够满足加氢裂化催化剂在低硫条件下的长周期稳定运行。
根据本发明的一个方面:加氢裂化反应条件包括温度300~450℃,氢气分压力2.0~10.0MPa,液相空速0.2~4.0小时-1,氢油体积比500~4000。在优选的条件下:加氢裂化反应条件包括温度320~420℃,氢气分压力5.0~9.0MPa,液相空速0.5~2.0小时-1,氢油体积比1000~3000。
根据本发明的一个方面:采用本发明的加氢裂化催化剂在上述加氢裂化反应条件下进行的加氢裂化反应,其200℃以上馏分单程转化率大于70重量%,包括轻质芳烃和C2-C5轻烃的化工料的总选择性大于80重量%。
根据本发明的一个方面:本发明所述催化剂在所述加氢裂化反应条件下,对所述原料油加氢裂化反应后的加氢裂化产物中,包括轻质芳烃和C2-C5轻烃化工料的总选择性大于80重量%。所述轻质芳烃是指碳数小于11的芳烃,包括C6芳烃,例如苯;C7芳烃,例如甲苯;C8芳烃,例如乙苯、二甲苯;C9芳烃,例如甲乙苯、丙苯、三甲苯;C10芳烃,例如四甲苯、二甲基乙基苯、二乙苯。所述C2-C5轻烃包括乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷等饱和轻烃。
本发明提供的一种化工型加氢裂化催化剂,可用于生产具有化工用途的轻质芳烃和轻烃,实现催化柴油等低值富芳油品向芳烃、烯烃等化工产品的转化。本发明的化工型加氢裂化催化剂中,采用硅铝比30-100的β沸石和薄片厚度仅为2-12nm的层状MWW型沸石的组合作为酸性功能组分。占优势的β沸石发挥主导性裂解作用,β沸石的孔道择形效应使四氢萘系烃类选择性转化为轻质芳烃,且使轻质芳烃馏分内的烷烃、环烷烃进一步裂解,所得的重石脑油的芳烃纯度能够满足芳烃联合装置的需求,同时大量副产C2-C5轻烃,作为烯烃原料。薄片状MWW结构沸石可实现对重稠环芳烃大分子的转化,在原料油转化过程中发生轻质化反应,减少了结焦前体的生成。该化工型加氢裂化催化剂表现出原料单程转化率高、轻质芳烃收率及纯度高、催化剂稳定性好的特点。
附图说明
图1本发明加氢裂化催化剂的所述β沸石的TEM图。
图2本发明加氢裂化催化剂的所述层状MWW型沸石的TEM图。
其中图1为本发明实施例2~5和实施例7所采用的β沸石的TEM图,颗粒尺寸介于200-500nm。
其中图2为本发明实施例所采用的层状MWW型沸石—SRZ-21沸石的TEM图,可观察到明显的层状结构,单层MWW结构的薄片厚度为2.6-2.7nm,还存在少量的双层或三层MWW结构,其薄片厚度约为5-9nm。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明和描述。但是需要指出的是,本发明的保护范围并不受此限制,而是由附录的权利要求书来确定。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在以下具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,由此而形成的技术方案属于本说明书原始公开内容的一部分,同时也落入本发明的保护范围,而不应被视为是本文未曾披露或预期过的新内容,除非本领域技术人员认为该结合是明显不合理的。
在本说明书的上下文中,除了明确说明的内容之外,未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都通过引用并入本文。除非另有定义,本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下,以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时,该词头导出的对象涵盖本申请提出时本领域常规使用的那些,但也包括目前还不常用,却将变成本领域公认为适用于类似目的的那些。
在没有明确指明的情况下,本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的,除非以重量为基准时不符合本领域技术人员的常规认识;温度的单位均为℃,压力为表压,所提到的空速为液时空速LHSV。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。在下文中,各个技术方案之间原则上可以相互组合而得到新的技术方案,这也应被视为在本文中具体公开。
本发明具体实施方式部分涉及到的测试方法和标准:
1、本发明中,通过ICP(电感耦合等离子体)和XRF(X射线荧光)方法分析催化剂的组成。用XPS(X射线光电子能谱)方法确定VIB族金属氧化物的组成比例。ICP测试条件为:Varian 700-ES系列XPS仪。XRF测试条件为:Rigaku ZSX 100e型XRF仪。XPS测试条件:Perkin Elmer PHI 5000C ESCA型X射线光电子能谱仪,使用Mg K激发光源,操作电压l0kV,电流40mA,真空度4.0×10-8Pa。
2、本发明中,通过气相色谱法测定原料油和轻质化产品组成。色谱型号为Agilent7890A,配备FID检测器,FFAP毛细管色谱柱进行分离,色谱柱采用程序升温,初始温度90℃,保持15分钟,然后以15℃/分钟速率升温至220℃,维持45分钟。采用GC-MS及GC-FID方法,分析加氢裂化产物中的四环及以上芳烃含量,对芘(四环)到晕苯(七环)的超重芳烃实现定量分析。
3、本发明中,孔道空间指数的测定方法如下:将特定氢型十二元环沸石负载0.1-0.5wt%的铂或钯贵金属后,用于丁基环己烷的加氢裂化反应,分析产物中的异丁烷和正丁烷的摩尔比,即为这种十二元环沸石的孔道空间指数。以此空间指数可以表征不同十二元环沸石孔道的开阔程度。
本发明具体实施方式部分涉及到的主要结果数据的计算依据:
1、总转化率(200℃以上馏分单程转化率)计算公式为:
2、化工料总选择性计算公式为:
3、在线运行200小时的活性衰减率:
本发明具体实施方式部分涉及到的原料:
1、为说明本发明效果,提供了两种具有代表性的原料油。原料组成见表1,原料油1和原料油2为加氢精制后的催化柴油。
2、本发明实施例和对比例涉及到的包括但不限于催化剂的原料均可市售而得。
表1
原料油1 | 原料油2 | |
密度(4℃) | 0.91 | 0.92 |
硫(wtppm) | 93 | 56 |
氮(wtppm) | 14.3 | 7.4 |
非芳香烃(wt) | 25.60 | 17.60 |
单环芳烃(wt%) | 50.08 | 70.27 |
稠环芳烃(wt%) | 24.32 | 12.13 |
初馏点 | 195 | 157 |
5% | 206 | 179 |
10% | 216 | 188 |
30% | 245 | 223 |
50% | 266 | 242 |
70% | 336 | 263 |
90% | 351 | 285 |
终馏点 | 365 | 325 |
>200℃馏分量(wt%) | 97 | 80 |
【对比例1】
氢型β沸石选自中国石化催化剂分公司的氢型β沸石,其硅铝比(SAR)为50.5,孔道空间指数为16.5,其透射电镜图(TEM)见图1。氢型β沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在550℃空气气氛中焙烧4小时,即得所需的催化剂载体。以硝酸镍和钨酸铵配制双金属水溶液,通过等体积浸渍方法浸渍上述催化剂载体,在120℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到450℃,保持4小时,即得到加氢裂化催化剂C0。以重量份数计,其组成为:3.5份Ni-12.5份WOx/62份β沸石-余量22份Al2O3,其中x值为2.43。
采用原料1为评价原料,反应条件为:温度390℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为93.20%,化工料总选择性为89.77%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为81.59%,化工料总选择性为83.23%。200h催化剂活性衰减率为12.46%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.55%(见表3)。
【实施例1】层状MWW型沸石制备:
本发明层状MWW型沸石选自中国石化催化剂分公司的SRZ-21沸石,具体制备如下(按CN101121524A说明书实施例1):
将铝酸钠(Al2O3 42.0重量%)6.1克溶于288克水中,加入氢氧化钠1.0克使之溶解,然后在搅拌的情况下加入六氢吡啶34.0克,再加入固体氧化硅60克,三甲基氯硅烷5.5克,反应物的物料配比(摩尔比)为:
SiO2/Al2O3=40
NaOH/SiO2=0.025
三甲基氯硅烷/SiO2=0.05,
六氢吡啶/SiO2=0.50
H2O/SiO2=16
待反应混合物搅拌均匀后,装入不锈钢反应釜中,在搅拌情况下于135℃晶化50小时。取出后经过滤、洗涤、干燥,得到SRZ-21沸石。经化学分析得SiO2/Al2O3摩尔比为42.1。
干燥后的样品经测定,其29Si MAS NMR固体核磁谱在15.1ppm出现核磁共振谱峰。其X-射线衍射数据见表2,具有MWW结构特征。
表2
以上SRZ-21沸石,其硅铝比为42.1。图2为该SRZ-21沸石TEM图,可观察到SRZ-21沸石具有明显的薄片结构,其中单层MWW结构的薄片厚度为2.6-2.7nm,还存在少量的双层或三层MWW结构,薄片厚度约为5-9nm。
【实施例2】
氢型β沸石原料同对比例1的β沸石;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
取以上所述氢型β沸石、SRZ-21沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在530℃空气气氛中焙烧2小时,即得所需的催化剂载体。以硝酸镍和钨酸铵配制双金属水溶液,通过等体积浸渍方法浸渍上述催化剂载体,在90℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到450℃,保持4小时,可得到本发明所述的加氢裂化催化剂C1。以重量份数计,其组成为:3.5份Ni-12.5份WOx/52份β沸石-10份SRZ-21-余量22份Al2O3,其中x值为2.41。
采用原料1为评价原料,反应条件为:温度375℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为93.81%,化工料总选择性为90.05%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为91.65%,化工料总选择性为86.41%。200h催化剂活性衰减率为2.30%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.27%。
【实施例3】
氢型β沸石原料同对比例1的β沸石;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
将所述氢型β沸石、SRZ-21沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在530℃空气气氛中焙烧2小时,即得所需的催化剂载体。以草酸钴、钨酸铵和钼酸铵配制三金属水溶液,通过等体积浸渍方法浸渍催化剂载体,在90℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到480℃,保持6小时,可得到本发明所述加氢裂化催化剂C2。以重量份数计,组成为:1.3份Co-5.8份WOx1-6.7份MoOx2/35份β沸石-15份SRZ-21-余量36.2份Al2O3,其中x1值为2.55,x2值为2.30。
采用原料1为评价原料,反应条件为:温度390℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为94.23%,化工料总选择性为91.45%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为92.61%,化工料总选择性为88.55%。200h催化剂活性衰减率为1.72%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.09%。
【实施例4】
氢型β沸石原料同对比例1的β沸石;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
将所述氢型β沸石、SRZ-21沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在530℃空气气氛中焙烧2小时,即得所需的催化剂载体。以氯化锌和钼酸铵配制双金属水溶液,通过等体积浸渍方法浸渍催化剂载体,在100℃烘干后在480℃空气气氛中焙烧3小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到500℃,保持4小时,可得到本发明所述加氢裂化催化剂C3。以重量份数计,组成为:3.8份Zn-13.5份MoOx/65份β沸石-5份SRZ-21-余量12.7份Al2O3,其中x值为2.09。
采用原料1为评价原料,反应条件为:温度370℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为95.07%,化工料总选择性为91.32%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为93.84%,化工料总选择性为89.47%。200h催化剂活性衰减率为1.29%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.20%。
【实施例5】
氢型β沸石原料同对比例1的β沸石;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
将所述氢型β沸石、SRZ-21沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在550℃空气气氛中焙烧3小时,即得所需的催化剂载体。硝酸铋溶于水中,采用等体积浸渍方法将其负载于催化剂载体上,在110℃烘干后在400℃空气气氛中焙烧3小时备用。以草酸镍、醋酸锌和钼酸铵配制三金属溶液,通过等体积浸渍方法浸渍上述负载铋的催化剂载体上,在100℃烘干后在500℃空气气氛中焙烧3小时得到催化剂前体。催化剂前体在氢气条件下还原到450℃,保持4小时,可得到本发明所述加氢裂化催化剂C4。以重量份数计,组成为:0.8份Zn-3.5份Ni-1.5份Bi-13.5份MoOx/35份β沸石-5份SRZ-21-余量40.7份Al2O3,其中x值为2.15。
采用原料1为评价原料,反应条件为:温度390℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为93.56%,化工料总选择性为89.99%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为90.27%,化工料总选择性为85.73%。200h催化剂活性衰减率为3.52%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.16%。
【实施例6】
氢型β沸石选自中国石化催化剂分公司的氢型β沸石,其硅铝比(SAR)为82.5,孔道空间指数为15.8;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
将所述氢型β沸石、SRZ-21沸石与多孔硅胶粉(SiO2含量大于99.9%wt)充分混合后,加入干基SiO2含量为30%的氨型硅溶胶混捏、挤条、120℃烘干后在600℃空气气氛中焙烧4小时,即得所需的催化剂载体。将四氯化锡溶于水中,采用等体积浸渍方法将其负载于催化剂载体上,在110℃烘干后在400℃空气气氛中焙烧2小时备用。以氯化钯和氯铂酸配制双金属水溶液,通过等体积浸渍方法浸渍上述负载锡的催化剂载体,在110℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到400℃,保持4小时,可得到所需的加氢裂化催化剂C5。以重量份数计,组成为:0.05份Pt-0.15份Pd-1.4份Sn/65份β沸石-5份SRZ-21-余量28.4份SiO2。
采用原料2为评价原料,反应条件为:温度360℃,压力6.0MPa,LHSV空速1.2小时-1,氢油体积比2000。稳定运行24小时后取样分析并计算,总转化率为96.35%,化工料总选择性为81.73%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为95.09%,化工料总选择性为80.92%。200h催化剂活性衰减率为1.31%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.07%。
【实施例7】
氢型β沸石原料同对比例1的β沸石;
层状MWW型沸石选自实施例1所制备的SRZ-21沸石。
取以上所述氢型β沸石、SRZ-21沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在530℃空气气氛中焙烧2小时,即得所需的催化剂载体。将四氯化锡溶于水中,采用等体积浸渍方法将其负载于催化剂载体上,在110℃烘干后在400℃空气气氛中焙烧2小时备用。以硝酸镍和钨酸铵配制双金属水溶液,通过等体积浸渍方法浸渍上述载锡催化剂载体,在90℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到450℃,保持4小时,可得到本发明所述的加氢裂化催化剂C6。以重量份数计,其组成为:3.4份Ni-1.8份Sn-12.3份WOx/51份β沸石-9.5份SRZ-21-余量22份Al2O3,其中x值为2.45。
采用原料1为评价原料,反应条件为:温度375℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为94.59%,化工料总选择性为92.05%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为92.87%,化工料总选择性为91.23%。200h催化剂活性衰减率为1.82%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.23%。
【对比例2】
氢型β沸石原料同对比例1的β沸石;
氢型MCM-22沸石取自中国石化催化剂分公司;氢型MCM-22沸石为典型的MWW型沸石,其颗粒的厚度尺寸约为1.5μm,其硅铝比为45。
取以上所述氢型β沸石、MCM-22沸石与拟薄水铝石充分混合后,混捏、挤条、120℃烘干后在530℃空气气氛中焙烧2小时,即得所需的催化剂载体。以硝酸镍和钨酸铵配制双金属水溶液,通过等体积浸渍方法浸渍上述催化剂载体,在90℃烘干后在500℃空气气氛中焙烧2小时得到催化剂前体。将所得催化剂前体在氢气条件下还原到450℃,保持4小时,可得到本发明所述的加氢裂化催化剂C7。以重量份数计,其组成为:3.5份Ni-12.5份WOx/52份β沸石-10份MCM-22-余量22份Al2O3,其中x值为2.40。
采用原料1为评价原料,反应条件为:温度375℃,压力8.5MPa,LHSV空速1.0小时-1,氢油体积比3000。稳定运行24小时后取样分析并计算,总转化率为90.15%,化工料总选择性为87.08%。维持反应条件和原料不变,在线运行200小时后取样分析并计算,总转化率为75.64%,化工料总选择性为81.05%。200h催化剂活性衰减率为16.10%。
进一步分析可得,在线200小时加氢裂化产物中的四环及以上超重芳烃的含量为0.53%。全部【对比例】和【实施例2~7】所得在线200小时加氢裂化产物中的四环及以上超重芳烃的含量数据汇总于表3。
表3
催化剂 | 超重芳烃含量,% |
C0 | 0.55 |
C1 | 0.27 |
C2 | 0.09 |
C3 | 0.20 |
C4 | 0.16 |
C5 | 0.07 |
C6 | 0.23 |
C7 | 0.53 |
Claims (17)
1.一种加氢裂化催化剂,包括以下组分:
a)β沸石、b)层状MWW型沸石、c)金属功能组分和d)粘结剂,以及任选的e)金属功能调节组分;其中层状MWW型沸石的薄片厚度范围为2-12nm;所述层状MWW型沸石选自SRZ-21沸石;所述金属功能组分为贵金属铂和/或钯;或者,所述金属功能组分为非硫化态的VIII族金属、IIB族金属中的至少一种与非硫化态的VIB族金属氧化物的组合;所述β沸石占总沸石量的50-99%wt;
以总沸石重量为100份计,所述的金属功能组分以元素为基础计为0.1~60份;和/或,所述粘结剂为5~2000份。
2.根据权利要求1所述催化剂,其特征在于,
以总沸石重量为100份计,所述的金属功能组分以元素为基础计为0.2~50份;和/或,所述粘结剂为10~1000份。
3.根据权利要求1所述催化剂,其特征在于,
所述β沸石占总沸石量的60-95%wt。
4.根据权利要求1所述催化剂,其特征在于,
所述β沸石硅铝比介于10~200;和/或,
所述β沸石孔道空间指数介于15~18;和/或,
所述层状MWW型沸石的薄片厚度范围为2-10nm;和/或,
所述层状MWW型沸石的硅铝比介于10~100;和/或,
所述粘结剂包括氧化铝、氧化硅中的一种。
5.根据权利要求4所述催化剂,其特征在于,
所述β沸石硅铝比介于30-100。
6.根据权利要求1所述催化剂,其特征在于,
以金属元素为基础计,其中VIB族金属与VIII族金属和IIB族金属之和的重量比为(0.2~20):1。
7.根据权利要求6所述催化剂,其特征在于,
以金属元素为基础计,其中VIB族金属与VIII族金属和IIB族金属之和的重量比为(0.3~15):1。
8.根据权利要求1所述催化剂,其特征在于,
所述VIII族金属包括钴、镍中的至少一种;和/或,
所述VIB族金属氧化物包括钼的氧化物和钨的氧化物中的至少一种;和/或,
所述IIB族金属包括锌。
9.根据权利要求8所述催化剂,其特征在于,
所述VIB族金属氧化物为二氧化钼、三氧化钼、二氧化钨、三氧化钨中的至少一种。
10.根据权利要求1所述催化剂,其特征在于,
所述催化剂含有金属功能调节组分时,以金属元素为基础,所述金属功能组分与金属功能调节组分的重量比为(0.1~20):1;和/或,
所述金属功能调节组分包括锡和/或铋。
11.根据权利要求10所述催化剂,其特征在于,
以金属元素为基础,所述金属功能组分与金属功能调节组分的重量比为(0.1~15):1。
12.根据权利要求1~11之任一项所述的加氢裂化催化剂的制备方法,包括将包含所述β沸石和层状MWW型沸石的催化剂载体成型并负载包括所述金属功能组分在内的组分得到催化剂前体,再将催化剂前体还原的步骤。
13.根据权利要求12所述的制备方法,其特征在于包括以下步骤:
1)将包括所述β沸石和层状MWW型沸石与所述粘结剂在内的组分混合干燥后在500~600℃空气气氛中焙烧得所需的催化剂载体;
2)以包括所述贵金属铂和/或钯的金属化合物,或者包括所述VIII族金属化合物及IIB族金属化合物的至少一种与所述VIB族金属化合物在内的金属组分,配制金属水溶液;通过等体积浸渍方法浸渍以上所得催化剂载体,干燥后在450~580℃空气气氛中焙烧得到催化剂前体;
3)将所得催化剂前体在氢气条件下还原到400~500℃,得到所述催化剂;
任选地,在上述步骤2)之前,将所述金属功能调节组分的金属化合物配制成金属水溶液,等体积浸渍步骤1)所得催化剂载体并干燥后在350℃~500℃空气气氛中焙烧。
14.一种加氢裂化催化剂在加氢裂化反应中的应用,包括将权利要求1-11之任一项所述的催化剂,或者权利要求12或13所述的制备方法所得的催化剂,在加氢裂化条件下与原料油接触的步骤。
15.根据权利要求14所述的应用,其特征在于,
所述原料油中芳烃重量百分比大于50重量%;和/或,
所述原料油中氮含量≤20ppm、硫含量≤200ppm。
16.根据权利要求14所述的应用,其特征在于,
所述加氢裂化反应条件包括:温度300~450℃,氢气分压力2.0~10.0MPa,液相空速0.2~4.0小时-1,氢油体积比500~4000。
17.根据权利要求14~16之任一项所述的应用,其特征在于200℃以上馏分单程转化率大于70重量%,包括轻质芳烃和C2-C5轻烃在内的化工料的总选择性大于80重量%。
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JP2023548790A (ja) | 2023-11-21 |
EP4230292A1 (en) | 2023-08-23 |
KR20230093292A (ko) | 2023-06-27 |
US20230390749A1 (en) | 2023-12-07 |
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