CN116490273A - 使用ssz-91的高纳米孔体积催化剂和工艺 - Google Patents
使用ssz-91的高纳米孔体积催化剂和工艺 Download PDFInfo
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- CN116490273A CN116490273A CN202180079198.5A CN202180079198A CN116490273A CN 116490273 A CN116490273 A CN 116490273A CN 202180079198 A CN202180079198 A CN 202180079198A CN 116490273 A CN116490273 A CN 116490273A
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- Prior art keywords
- catalyst
- range
- pore size
- pore volume
- alumina
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000011148 porous material Substances 0.000 claims abstract description 139
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002199 base oil Substances 0.000 claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 239000001993 wax Substances 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000010724 circulating oil Substances 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000010913 used oil Substances 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 42
- 239000002585 base Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052800 carbon group element Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910021476 group 6 element Inorganic materials 0.000 description 2
- 229910021474 group 7 element Inorganic materials 0.000 description 2
- 229910021472 group 8 element Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 nitrogen containing hydrocarbon Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B01J35/615—100-500 m2/g
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- B01J35/638—Pore volume more than 1.0 ml/g
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
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Abstract
一种用于制备基础油产物的改进的加氢异构化催化剂和工艺,其中所述催化剂包含含有SSZ‑91分子筛和高纳米孔体积氧化铝的基础挤出物。所述催化剂和工艺一般涉及使用SSZ‑91/高纳米孔体积氧化铝基催化剂来通过使该催化剂与烃原料接触而生产脱蜡基础油产物。所述催化剂基础挤出物有利地包含具有0.05至1.0cc/g的在11‑20nm孔径范围内的孔体积的氧化铝,其中由SSZ‑91和氧化铝形成的基础挤出物具有0.12至1.80cc/g的在2‑50nm孔径范围内的总孔体积。所述催化剂和工艺在减少气体和燃料产生的同时提高了基础油产率。
Description
相关申请的交叉引用
本申请要求2020年11月11日提交的美国专利申请序列号17/095,010的优先权权益,其公开内容以全文并入本文。
技术领域
一种加氢异构化催化剂和使用包含SSZ-91分子筛和高纳米孔体积氧化铝的基础挤出物的催化剂由烃原料生产基础油的工艺。
背景技术
由烃原料生产基础油的加氢异构化催化脱蜡工艺包括在氢气存在下将原料引入到含有脱蜡催化剂体系的反应器中。在反应器内,进料在加氢异构化脱蜡条件下与加氢异构化催化剂接触以提供异构化料流。加氢异构化去除芳烃和残余的氮和硫并且使正链烷烃异构化以改进冷流特性。异构化料流可进一步在第二反应器中与加氢精制催化剂接触以从基础油产物中去除痕量的任何芳烃、烯烃,改进颜色等。加氢精制单元可包括加氢精制催化剂,该加氢精制催化剂包括氧化铝载体和贵金属,通常为钯,或铂与钯的组合。
在典型的加氢异构化催化脱蜡工艺中一般面临的挑战包括,尤其是所提供的一种或多种产物要满足相关产品规格(诸如一种或多种产物的浊点、倾点、粘度和/或粘度指数限值),同时还要维持良好的产物产率。此外,例如在加氢精制期间,为了进一步提高产物质量,可使用进一步的升级,例如通过使芳烃饱和以降低芳烃含量来获得颜色和氧化稳定性。然而,来自上游加氢处理和加氢裂化过程的残余有机硫和氮的存在可能对下游过程和最终基础油产物质量具有显著影响。
直链链烷烃的脱蜡涉及许多加氢转化反应,包括加氢异构化、支链的重新分布和二次加氢异构化。连续的加氢异构化反应导致支化程度增加伴随着支链的重新分布。增加的支化一般会使链裂化的可能性增加,从而导致更大的燃料产率,和基础油/润滑油产率的损失。因此,使此类反应(包括加氢异构化过渡物质的形成)最小化可导致基础油/润滑油产率增加。
因此,需要用于基础油/润滑油生产的更稳健的催化剂,以对蜡分子进行异构化并且通过减少不期望的裂化和加氢异构化反应来提供增加的基础油/润滑油产率。因此,持续需要用于生产具有减少的燃料产生、同时还提供良好的基础油/润滑油产物产率的基础油/润滑油产物的催化剂和工艺。
发明内容
本发明涉及一种用于将含蜡烃原料转化为通常具有增加的基础油产物产率的高级产物(包括基础油或润滑油)的加氢异构化催化剂和工艺。此类工艺使用包含由SSZ-91分子筛和高纳米孔体积(HNPV)氧化铝的混合物形成的基础挤出物的催化剂体系。所述加氢异构化工艺将脂族未支化链烷烃(正链烷烃)转化为异链烷烃和环状物质,从而使基础油产物的倾点和浊点与原料相比降低。已经发现由SSZ-91/HNPV氧化铝的基础挤出物形成的催化剂有利地提供与使用其他催化剂生产的基础油产物相比具有增加的基础油/润滑油产物产率的基础油产物。
在一方面,本发明涉及一种加氢异构化催化剂和工艺,该加氢异构化催化剂和工艺可用于通过对合适的烃进料流进行加氢加工来制备包括基础油在内的脱蜡产物,特别是一个或多个产品级的基础油产物。虽然不必限于此,但本发明的目的之一是提供增加的基础油产物产率,同时还减少气体和燃料级产物的产生。
该催化剂一般包含含有SSZ-91分子筛和HNPV氧化铝的基础挤出物以及至少一种选自周期表第6至10族和第14族的改性剂,其中该氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积并且该基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积。
该工艺一般包括使烃进料与加氢异构化催化剂在加氢异构化条件下接触以产生产物或产物料流。该加氢异构化催化剂包含SSZ-91分子筛和HNPV氧化铝以及至少一种选自周期表第6至10族和第14族的改性剂,其中该氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积并且该基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积。
具体实施方式
尽管本文提供了一个或多个方面的说明性实施方案,但所公开的工艺可使用许多技术来实现。本公开不限于本文例示的例示性或特定实施方案、附图和技术(包括本文例示和描述的任何示例性设计和实施方案),并且可以在所附权利要求的范围及其等效物的全部范围内进行修改。
除非另有说明,以下术语、术语和定义适用于本公开。如果在本公开中使用术语,但在本文中没有具体定义,则可应用来自IUPAC化学术语汇编,第2版(1997)的定义,条件是该定义不与本文中应用的任何其他公开或定义冲突,或没有使应用该定义的任何权利要求变得不明确或不可行。如果通过引用并入本文的任何文件所提供的任何定义或用法与本文提供的定义或用法相冲突,则应理解本文提供的定义或用法适用。
“API比重”是指石油原料或产物相对于水的比重,如通过ASTM D4052-11确定。
“粘度指数”(VI)表示润滑剂的温度依赖性,如通过ASTM D2270-10(E2011)确定。
“真空瓦斯油”(VGO)是原油真空蒸馏的副产物,其可被送至加氢加工单元或送至芳烃抽提以升级为基础油。VGO一般包含在0.101MPa下沸程分布在343℃(649℉)和593℃(1100℉)之间的烃。
当与油原料结合使用时,“处理”、“经处理的”、“升级(upgrade、upgrading)”和“经升级(upgraded)”描述了正在或已经经受加氢加工的原料,或产生的材料或粗产物,该材料或粗产物具有原料分子量的降低、原料沸点范围的降低、沥青质浓度的降低、烃自由基浓度的降低和/或杂质(诸如硫、氮、氧、卤化物和金属)的量的降低。
“加氢加工(Hydroprocessing)”是指在较高的温度和压力下使含碳原料与氢气和催化剂接触,目的是去除不期望的杂质和/或将原料转化成期望产物的工艺。加氢加工工艺的实例包括加氢裂化、加氢处理、催化脱蜡和加氢精制。
“加氢裂化”是指其中氢化和脱氢伴随烃的裂化/片段化的工艺,如,将较重的烃转化为较轻的烃,或将芳烃和/或环链烷烃(环烷属烃)转化为非环状支化链烷烃的工艺。
“加氢处理”是指将含硫和/或氮的烃进料转化为具有降低的硫和/或氮含量的烃产物(通常与加氢裂化结合)并且(分别)产生硫化氢和/或氨作为副产物的工艺。在氢气存在下执行的此类工艺或步骤包括烃原料组分(例如,杂质)的加氢脱硫、加氢脱氮、加氢脱金属和/或加氢脱芳构化,和/或用于原料中不饱和化合物的氢化。根据加氢处理的类型和反应条件,加氢处理工艺的产物可以具有例如改进的粘度、粘度指数、饱和物含量、低温性能、挥发性和去极化。术语“防护层”和“防护床”在本文中可同义地且可互换地用于指加氢处理催化剂或加氢处理催化剂层。防护层可以是用于烃脱蜡的催化剂体系的组分,并且可被设置在至少一种加氢异构化催化剂的上游。
“催化脱蜡”或加氢异构化是指通过在氢气存在下与催化剂接触将正链烷烃异构化为其更支化的对应物的工艺。
“加氢精制”是指旨在通过去除痕量芳烃、烯烃、发色体和溶剂来改善加氢精制产物的氧化稳定性、UV稳定性和外观的工艺。UV稳定性是指在暴露于UV光和氧气中时被测试的烃的稳定性。当形成可见的沉淀物时,通常看起来像是Hoc或浑浊,或在暴露于紫外光和空气中后产生较暗的颜色时,则表明不稳定。加氢精制的一般描述可见于美国专利号3,852,207和4,673,487。
术语“氢(Hydrogen或hydrogen)”是指氢本身,和/或提供氢源的一种或多种化合物。
“BET表面积”通过在其沸腾温度下的N2吸附确定。BET表面积通过5点法在P/P0=0.050、0.088、0.125、0.163和0.200下计算。首先将样品在流动的干燥N2存在下在400℃下预处理6小时以消除任何吸附的挥发物,例如水或有机物。
“切割点”是指在达到预定分离程度时真实沸点(ΤΒΡ)曲线上的温度。
“倾点”是指油在受控条件下开始流动时的温度。倾点可通过例如ASTM D5950确定。
“浊点”是指润滑油基础油样品随着该油在具体指定条件下冷却而开始出现浑浊时的温度。润滑油基础油的浊点与其倾点互补。浊点可通过例如ASTM D5773确定。
“纳米孔直径”和“纳米孔体积”通过在其沸腾温度下的N2吸附确定,并且通过以下文献中描述的BJH方法由N2等温线计算:E.P.Barrett,L.G.Joyner和P.P.Halenda,"Thedetermination of pore volume and area distributions in poroussubstances.I.Computations from nitrogen isotherms."J.Am.Chem.Soc.73,373–380,1951。首先将样品在流动的干燥N2存在下在400℃下预处理6小时以消除任何吸附的挥发物,例如水或有机物。总纳米孔体积的10%、50%和90%处的孔径,分别称为d10、d50和d90,也可由此类N2吸附测量来确定。
“TBP”是指含烃进料或产物的沸点,如通过ASTM D2887-13由模拟蒸馏(SimDist)确定。
“含烃”、“烃”和类似术语是指仅含有碳和氢原子的化合物。其他标识符可用于指示在烃中存在特定基团(如果有的话)(如,卤代烃指示存在代替烃中等同数目的氢原子的一个或多个卤素原子)。
术语“周期表”是指IUPAC元素周期表2007年6月22日的版本,并且周期表组的编号方案是如Chem.Eng.News,63(5),26-27(1985)中所述。“第2族”是指IUPAC第2族元素,例如呈元素、化合物或离子形式中的任一形式的镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)以及它们的组合。“第6族”是指IUPAC第6族元素,例如铬(Cr)、钼(Mo)和钨(W)。“第7族”是指IUPAC第7族元素,例如呈元素、化合物或离子形式中的任一形式的锰(Mn)、铼(Re)以及它们的组合。“第8族”是指IUPAC第8族元素,例如呈元素、化合物或离子形式中的任一形式的铁(Fe)、钌(Ru)、锇(Os)以及它们的组合。“第9族”是指IUPAC第9族元素,例如呈元素、化合物或离子形式中的任一形式的钴(Co)、铑(Rh)、铱(Ir)以及它们的组合。“第10族”是指IUPAC第10族元素,例如呈元素、化合物或离子形式中的任一形式的镍(Ni)、钯(Pd)、铂(Pt)以及它们的组合。“第14族”是指IUPAC第14族元素,例如呈元素、化合物或离子形式中的任一形式的锗(Ge)、锡(Sn)、铅(Pb)以及它们的组合。
术语“载体”,特别是如在术语“催化剂载体”中使用,是指通常为具有高表面积的固体的常规材料,催化剂材料附着于其上。载体材料可以是惰性的或参与催化反应,并且可以是多孔的或无孔的。典型的催化剂载体包括各种碳、氧化铝、二氧化硅和二氧化硅-氧化铝,例如无定形二氧化硅铝酸盐、沸石、氧化铝-氧化硼、二氧化硅-氧化铝-氧化镁、二氧化硅-氧化铝-二氧化钛和通过向前述材料中添加其他沸石和其他复合氧化物获得的材料。
“分子筛”是指这样的材料,该材料在骨架结构内具有均匀的分子尺寸的孔,使得根据分子筛的类型,只有某些分子可以进入分子筛的孔结构,而其他分子则例如由于分子尺寸和/或反应性而被排除。术语“分子筛”和“沸石”是同义的并且包括(a)中间体和(b)最终或目标分子筛以及通过(1)直接合成或(2)结晶后处理(次级改性)产生的分子筛。次级合成技术允许通过杂原子晶格取代或其他技术从中间体材料合成目标材料。例如,铝硅酸盐可由中间体硼硅酸盐通过Al对B的结晶后杂原子晶格取代来合成。此类技术是已知的,例如如美国专利号6,790,433中所述。沸石、结晶磷酸铝和结晶硅磷酸铝是分子筛的代表性示例。
在本公开中,尽管组合物和方法或工艺通常以“包含”各种组分或步骤的形式描述,但除非另有说明,否则组合物和方法也可以“基本上由各种组分或步骤组成”或“由各种组分或步骤组成”。
术语“一个”、“一种”和“该/所述”旨在包括多个替代物,例如至少一个/种。例如,除非另外指明,否则“过渡金属”或“碱金属”的公开意在涵盖一种过渡金属或碱金属,或多于一种过渡金属或碱金属的混合物或组合。
本文的详细说明和权利要求书中的所有数值均由“大约”或“近似”所指示的值来修饰,并且考虑本领域普通技术人员所预期的实验误差和变化。
在一方面,本发明是一种可用于制备包含基础/润滑油的脱蜡产物的加氢异构化催化剂,该催化剂包含由SSZ-91分子筛和氧化铝形成的基础挤出物以及至少一种选自周期表第6至10族和第14族的改性剂,其中该氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积,并且该基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积。
在进一步的方面,本发明涉及一种可用于制备包括基础油的脱蜡产物的加氢异构化工艺,该工艺包括使烃进料与加氢异构化催化剂在加氢异构化条件下接触以产生产物或产物料流;其中,该加氢异构化催化剂包含由SSZ-91分子筛和氧化铝形成的基础挤出物以及至少一种选自周期表第6至10族和第14族的改性剂,其中该氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积并且该基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积。
加氢异构化催化剂和工艺中使用的SSZ-91分子筛描述于例如美国专利号9,802,830、9,920,260、10,618,816和WO2017/034823中。SSZ-91分子筛一般包含ZSM-48型沸石材料,该分子筛具有总ZSM-48型材料的至少70%多型体6;0重量%与3.5重量%之间的量的EUO型相;以及多晶聚集体形态,该多晶聚集体形态包含具有在1与8之间的平均纵横比的微晶。SSZ-91分子筛的氧化硅与氧化铝摩尔比可在40至220或50至220或40至200的范围内。在一些情况下,SSZ-91材料由产物中存在的总ZSM-48型材料的至少90%多型体6组成。多型体6结构已由国际沸石协会的结构委员会给出了框架代码*MRE。术语“*MRE型分子筛”和“EUO型分子筛”包括国际沸石协会框架中指定的所有分子筛及其同型,如Atlas of ZeoliteFramework Types,编者Ch.Baerlocher,L.B.Mccusker和D.H.Olson,Elsevier,第6修订版,2007和国际沸石协会网站上的沸石结构数据库(http://www.iza-online.org)所述。
前述指出的专利提供了关于SSZ-91分子筛、其制备方法和由其形成的催化剂的额外细节。
加氢异构化催化剂和工艺中使用的氧化铝一般称为“高纳米孔体积”氧化铝,其在本文缩写为“HNPV”氧化铝。HNPV氧化铝可根据其在平均孔径范围内的孔体积方便地表征。本文缩写为“NPV”的术语“纳米孔体积”提供了方便的标签来定义氧化铝的孔体积范围和在那些范围内的值,例如在6-11nm孔径范围、11-20nm孔径范围和20-50nm孔径范围内的NPV孔体积。一般来说,氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积,或更特别地,0.07至0.85cc/g的在11-20nm孔径范围内的孔体积,或0.09至0.7cc/g的在11-20nm孔径范围内的孔体积。独立地,或除了前述11-20nm范围之外,氧化铝可具有0.05至1.0cc/g的在6-11nm孔径范围内的孔体积,或0.06至0.8cc/g的在6-11nm孔径范围内的孔体积,或0.07至0.6cc/g的在6-11nm孔径范围内的孔体积。独立地,或除了前述6-11nm和11-20nm范围之外,氧化铝可具有0.05至1.0cc/g的在20-50nm孔径范围内的孔体积,或0.07至0.8cc/g的在20-50nm孔径范围内的孔体积,或0.09至0.6cc/g的在20-50nm孔径范围内的孔体积。
氧化铝也可以以其在孔径范围内的总孔体积来表征。例如,除了前述NPV孔体积之外,或单独地和独立地,氧化铝可具有0.3至2.0cc/g的在2-50nm孔径范围内的总孔体积,或0.5至1.75cc/g的在2-50nm孔径范围内的总孔体积,或0.7至1.5cc/g的在2-50nm孔径范围内的总孔体积。
包含由SSZ-91筛/HNPV氧化铝形成的基础挤出物的催化剂一般还包含至少一种选自周期表(IUPAC)第6族至第10族和第14族的改性剂。合适的第6族改性剂包括第6族元素,例如呈元素、化合物或离子形式中的任一形式的铬(Cr)、钼(Mo)和钨(W)以及它们的组合。合适的第7族改性剂包括第7族元素,例如呈元素、化合物或离子形式中的任一形式的锰(Mn)、铼(Re)以及它们的组合。合适的第8族改性剂包括第8族元素,例如呈元素、化合物或离子形式中的任一形式的铁(Fe)、钌(Ru)、锇(Os)以及它们的组合。合适的第9族改性剂包括第9族元素,例如呈元素、化合物或离子形式中的任一形式的钴(Co)、铑(Rh)、铱(Ir)以及它们的组合。合适的第10族改性剂包括第10族元素,例如呈元素、化合物或离子形式中的任一形式的镍(Ni)、钯(Pd)、铂(Pt)以及它们的组合。合适的第14族改性剂包括第14族元素,例如呈元素、化合物或离子形式中的任一形式的锗(Ge)、锡(Sn)、铅(Pb)以及它们的组合。此外,可存在任选的第2族改性剂,包括第2族元素,例如呈元素、化合物或离子形式中的任一形式的镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)以及它们的组合。
改性剂有利地包含一种或多种第10族金属。第10族金属可以是例如铂、钯或它们的组合。在一些方面,铂是合适的第10族金属以及另一种第6至10族和第14族金属。尽管不限于此,但第6至10族和第14族金属可更窄地选自Pt、Pd、Ni、re、Ru、Ir、Sn或它们的组合。与作为催化剂中的第一金属的Pt相结合,催化剂中的任选第二金属也可更窄地选自第6至10族,并且第14族金属选自Pd、Ni、Re、Ru、Ir、Sn或它们的组合。在更具体的情况下,催化剂可包含0.01-5.0重量%或0.01-2.0重量%或0.1-2.0重量%、更特别地0.01-1.0重量%或0.3-0.8重量%的量的作为第10族金属的Pt。选自作为第6至10族和第14族金属的Pd、Ni、Re、Ru、Ir、Sn或它们的组合的任选第二金属可以以0.01-5.0重量%或0.01-2.0重量%,或0.1-2.0重量%、更特别地0.01-1.0重量%和0.01-1.5重量%的量存在。
催化剂中的金属含量可在有用的范围内变化,例如催化剂的总改性金属含量可为0.01-5.0重量%或0.01-2.0重量%或0.1-2.0重量%(基于总催化剂重量)。在一些情况下,催化剂包含0.1-2.0重量%的作为改性金属之一的Pt和0.01-1.5重量%的选自第6至10族和第14族的第二金属,或0.3-1.0重量%的Pt和0.03-1.0重量%的第二金属,或0.3-1.0重量%的Pt和0.03-0.8重量%的第二金属。在一些情况下,第一第10族金属与选自第6至10族和第14族的任选第二金属的比率可在5:1至1:5,或3:1至1:3,或1:1至1:2,或5:1至2:1,或5:1至3:1,或1:1至1:3,或1:1至1:4的范围内。
催化剂可进一步包含选自氧化铝、二氧化硅、二氧化铈、二氧化钛、氧化钨、氧化锆或它们的组合的额外基质材料。在更具体的情况下,第一催化剂包含0.01重量%至5.0重量%的改性金属、1重量%至99重量%的基质材料和0.1重量%至99重量%的SSZ-91分子筛/HNPV氧化铝基础挤出物。还可更窄地描述催化剂,例如催化剂可包含0.01重量%至5.0重量%的改性剂、15重量%至85重量%的基质材料和15重量%至85重量%的SSZ-91分子筛。可使用多于一种基质材料,例如,该基质材料可包含约15重量%-65重量%的第一基质材料和约15重量%-65重量%的第二基质材料。在此类情况下,第一基质材料和第二基质材料一般在一个或多个特征(诸如材料类型或孔体积和孔分布特征)上不同。当使用一种或多种基质材料时,第一基质材料、第二(和任何其他)基质材料也可以是相同类型的基质材料,例如,该基质材料可包含一种或多种氧化铝。
催化剂基础挤出物还适宜地通过孔体积在某些平均孔径范围内的总孔体积和孔体积方面两者来表征。与HNPV氧化铝一样,基础挤出物可根据在6-11nm孔径范围、在11-20nm孔径范围和在20-50nm孔径范围内的孔体积来表征。一般来说,基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积,或更特别地,0.20至1.65cc/g的在2-50nm孔径范围内的总孔体积,或0.25至1.50cc/g的在2-50nm孔径范围内的总孔体积。
独立地,或除了前述总孔体积2-50nm范围之外,基础挤出物可具有0.05至0.80cc/g的在6-11nm孔径范围内的孔体积,或0.08至0.60cc/g的在6-11nm孔径范围内的孔体积,或0.10至0.50cc/g的在6-11nm孔径范围内的孔体积。独立地,或除了前述6-11nm孔体积和2-50nm总孔体积范围之外,基础挤出物可具有0.05至0.80cc/g的在11-20nm孔径范围内的孔体积,或在0.08至0.60cc/g的11-20nm孔径范围内的孔体积,或0.10至0.50cc/g的在11-20nm孔径范围内的孔体积。独立地,或除了前述6-11nm和11-20nm孔体积范围和2-50nm总孔体积范围之外,基础挤出物可具有0.02至0.35cc/g的在20-50nm孔径范围内的孔体积,或0.03至0.30cc/g的在20-50nm孔径范围内的孔体积,或0.05至0.25cc/g的在20-50nm孔径范围内的孔体积。
基础挤出物可根据任何合适的方法制备。例如,基础挤出物可通过将组分混合在一起并且挤出充分混合的SSZ-91/HNPV氧化铝基础材料以形成基础挤出物来方便地制备。接下来将挤出物干燥并煅烧,随后将任何改性剂加载到基础挤出物上。可使用合适的浸渍技术将改性剂分散到基础挤出物上。然而,制备基础挤出物的工艺不旨在根据具体的工艺条件或技术而受到特别的限制。
烃进料一般可选自多种基础油原料,并且有利地包含瓦斯油;真空瓦斯油;久沸残渣(long residue);真空残渣;常压馏出物;重质燃料;油;蜡和石蜡;用过的油;脱沥青残渣或原油;由热转化或催化转化过程产生的装料(charges);页岩油;循环油;动物和植物来源的脂肪、油和蜡;石油和疏松蜡;或它们的组合。烃进料还可包含在400-1300℉,或500-1100℉,或600-1050℉的蒸馏范围内的进料烃馏分(cut),以及/或者其中烃进料具有约3至30cSt或约3.5至15cSt的KV100(在100℃下的运动粘度)范围。
在一些情况下,该工艺可被有利地用于作为烃进料的轻质或重质中性基础油原料(诸如真空瓦斯油(VGO)),其中SSZ-91/HNPV氧化铝催化剂包含Pt改性金属,或Pt与另一种改性剂的组合。
一种或多种产物,或产物料流可被用于生产一种或多种基础油产物,例如生产具有在约2至30cSt范围内的KV100的多等级物(multiple grade)。在一些情况下,此类基础油产物可具有不超过约-5℃,或-12℃,或-14℃的倾点。
该工艺和系统还可与额外的工艺步骤或系统部件组合,例如,可在使烃进料与SSZ-91/HNPV氧化铝加氢异构化催化剂接触之前用加氢处理催化剂使原料进一步经受加氢处理条件,任选地,其中该加氢处理催化剂包含防护层催化剂,该防护层催化剂包含含有约0.1至1重量%Pt和约0.2至1.5重量%Pd的难熔无机氧化物材料。
本发明工艺和催化剂体系提供的优点之一是使用包含SSZ-91分子筛和HNPV氧化铝(下文称为“SSZ-91/HNPV氧化铝”催化剂)的本发明催化剂体系生产的基础油产物的产率与使用包含SSZ-91分子筛和氧化铝的类似催化剂(下文称为“SSZ-91/氧化铝”催化剂)的相同工艺相比有所提高,该类似催化剂不含具有0.05至1.0cc/g(或在更特定情况下0.07至0.85cc/g,或0.09至0.70cc/g)的在11-20nm孔径范围内的孔体积的HNPV氧化铝组分。此外,在一些情况下,使用本发明的SSZ-91/HNPV氧化铝催化剂时的基础油产率与在相同工艺中使用此种类似的SSZ-91/氧化铝催化剂时的基础油产率相比显著增加了至少约0.5重量%或1.0重量%。本发明的SSZ-91/HNPV氧化铝催化剂和工艺还提供了与同样类似的SSZ-91/氧化铝催化剂相比产生较少的燃料和气体的额外益处。
在实践中,加氢脱蜡主要被用于通过从基础油中去除蜡来降低基础油的倾点和/或降低基础油的浊点。典型地,脱蜡使用催化工艺加工蜡,一般在脱蜡之前对脱蜡器进料进行升级以增加粘度指数,降低芳烃和杂原子含量,并且减少脱蜡器进料中低沸点组分的量。一些脱蜡催化剂通过将蜡质分子裂化成较低分子量分子来完成蜡转化反应。其他脱蜡工艺可通过蜡异构化将烃进料中所含的蜡转化至该过程,以产生倾点低于非异构化分子对应物的异构化分子。如本文所用,异构化包括在催化加氢异构化条件下在蜡分子的异构化中使用氢气的加氢异构化工艺。
合适的加氢脱蜡条件一般取决于所用的进料、所用的催化剂、期望的产率和期望的基础油特性。典型条件包括500℉至775℉(260℃至413℃)的温度;15psig至3000psig(0.10MPa至20.68MPa表压)的压力;0.25hr-1至20hr-1的LHSV;和2000SCF/bbl至30,000SCF/bbl(356至5340m3 H2/m3进料)的氢气与进料比率。一般地,将氢气从产物中分离并再循环至异构化区。一般地,本发明的脱蜡工艺在氢气存在下执行。典型地,氢气与烃的比率可在约2000至约10,000标准立方英尺H2/桶烃,并且通常约2500至约5000标准立方英尺H2/桶烃的范围内。以上条件可适用于加氢处理区的加氢处理条件以及第一催化剂和第二催化剂的加氢异构化条件。合适的脱蜡条件和工艺描述于例如美国专利号5,135,638、5,282,958和7,282,134中。
合适的催化剂体系一般包括包含SSZ-91/HNPV氧化铝催化剂的催化剂,该催化剂被布置成使得原料在进一步加氢精制步骤之前与SSZ-91/HNPV氧化铝催化剂接触。SSZ-91/HNPV氧化铝催化剂可单独使用,与其他催化剂组合使用,和/或用于层状催化剂体系中。可包括额外的处理步骤和催化剂,例如,如所指出的,一个或多个加氢处理催化剂/步骤、防护层和/或一个或多个加氢精制催化剂/步骤。
实施例
SSZ-91是根据US 10,618,816合成的,并且氧化铝是作为来自Sasol的氧化铝和/>氧化铝以及来自UOP的/>氧化铝提供的。SSZ-91分子筛具有120或更低的二氧化硅与氧化铝比率(SAR)。实施例中使用的氧化铝特性示于表1中。
表1
实施例1-加氢异构化催化剂A的制备
对比加氢异构化催化剂A如下制备:将微晶SSZ-91与表1的常规非HNPV氧化铝复合以提供含有65重量%SSZ-91沸石的混合物。将混合物挤出、干燥和煅烧,并将经干燥和煅烧的挤出物用含有铂的溶液浸渍。总铂负载量为0.6重量%。
实施例2-加氢异构化催化剂B的制备
如针对催化剂A所描述的那样制备加氢异构化催化剂B,以提供含有65重量%SSZ-91和35重量%HNPV氧化铝I的混合物。将经干燥和煅烧的挤出物用铂浸渍以提供0.6重量%的总铂负载量。
实施例3-加氢异构化催化剂C的制备
如针对催化剂A所描述的那样制备对比加氢异构化催化剂C,以提供含有45重量%SSZ-91和55重量%常规非HNPV氧化铝的混合物。将经干燥和煅烧的挤出物用铂浸渍以提供0.325重量%的总铂负载量。
实施例4-加氢异构化催化剂D的制备
如针对催化剂A所描述的那样制备加氢异构化催化剂D,以提供含有45重量%SSZ-91和55重量%HNPV氧化铝I的混合物。将经干燥和煅烧的挤出物用铂浸渍以提供0.325重量%的总铂负载量。
实施例5-加氢异构化催化剂E的制备
如针对催化剂A所描述的那样制备加氢异构化催化剂E,以提供含有45重量%SSZ-91、20重量%HNPV氧化铝I和35重量%HNPV氧化铝II的混合物。将经干燥和煅烧的挤出物用铂浸渍以提供0.325重量%的总铂负载量。
催化剂A至E的组成细节总结于表2中。
表2
催化剂A至E的孔径、孔体积和催化剂表面积细节总结于表3中。
表3
实施例6-催化剂A-B的加氢异构化性能
使用催化剂A和B对具有表4所示特性的轻质中性真空瓦斯油(VGO)加氢裂化原料进行加氢异构化。
表4
加氢异构化反应在配备有两个固定床反应器的微型单元中执行。该运行在2100psig总压力下操作。使进料以2的液时空速(LHSV)通过装有表2-表3中所列的催化剂A或B之一的加氢异构化反应器。然后在加载有加氢精制催化剂的第二反应器中对加氢异构化产物进行加氢精制以进一步改进润滑油产物质量(如US 8790507B2中所述)。加氢精制催化剂由Pt、Pd和载体组成。将加氢异构化反应温度调节在580-680℉的范围内。
氢与油比率约为3000scfb。将润滑油产物通过蒸馏段与燃料分离。基于SSZ-91/非HNPV氧化铝基础挤出物的对比催化剂A和由SSZ-91/HNPV氧化铝基础挤出物形成的催化剂B的润滑油产物产率示于表5中。
表5
与具有非HNPV基础挤出物组分的催化剂A相比,具有HNPV基础挤出物组分的催化剂B显示出约1重量%基础油/润滑油产物的增加。与非HNPV比较催化剂A相比,催化剂B还产生较少的燃料和气体。
本发明的一个或多个实施方案的前述描述主要是为了说明的目的,应该认识到可以使用仍然并入了本发明的本质的变化。在确定本发明的范围时,应该参考所附权利要求书。
出于美国专利实践的目的,以及在允许的其他专利局中,在本发明的前述描述中引用的所有专利和出版物都通过引用并入本文,只要其中包含的任何信息与前述公开内容一致和/或补充前述公开内容。
Claims (22)
1.一种可用于制备包括基础油的脱蜡产物的加氢异构化催化剂,所述加氢异构化催化剂包含
包含SSZ-91分子筛和氧化铝的基础挤出物,其中所述氧化铝具有0.05至1.0cc/g的在11-20nm孔径范围内的孔体积并且所述基础挤出物具有0.12至1.80cc/g的在2-50nm孔径范围内的总孔体积;以及
至少一种选自周期表第6至10族和第14族的改性剂。
2.如权利要求1所述的催化剂,其中所述改性剂包含周期表第8族至第10族金属。
3.如权利要求2所述的催化剂,其中所述改性剂是包含Pt的第10族金属。
4.如权利要求1所述的催化剂,其中所述氧化铝具有0.05至1.0cc/g的在6-11nm孔径范围内的孔体积,或0.06至0.8cc/g的在6-11nm孔径范围内的孔体积,或0.07至0.6cc/g的在6-11nm孔径范围内的孔体积。
5.如权利要求1所述的催化剂,其中所述氧化铝具有0.07至0.85cc/g的在11-20nm孔径范围内的孔体积,或0.09至0.7cc/g的在11-20nm孔径范围内的孔体积。
6.如权利要求1所述的催化剂,其中所述氧化铝具有0.05至1.0cc/g的在20-50nm孔径范围内的孔体积,或0.07至0.8cc/g的在20-50nm孔径范围内的孔体积,或0.09至0.6cc/g的在20-50nm孔径范围内的孔体积。
7.如权利要求1所述的催化剂,其中所述氧化铝具有0.3至2.0cc/g的在2-50nm孔径范围内的总孔体积,或0.5至1.75cc/g的在2-50nm孔径范围内的总孔体积,或0.7至1.5cc/g的在2-50nm孔径范围内的总孔体积。
8.如权利要求1所述的催化剂,其中所述基础挤出物具有0.05至0.80cc/g的在6-11nm孔径范围内的孔体积,或0.08至0.60cc/g的在6-11nm孔径范围内的孔体积,或0.10至0.50cc/g的在6-11nm孔径范围内的孔体积。
9.如权利要求1所述的催化剂,其中所述基础挤出物具有0.05至0.80cc/g的在11-20nm孔径范围内的孔体积,或0.08至0.60cc/g的在11-20nm孔径范围内的孔体积,或0.10至0.50cc/g的在11-20nm孔径范围内的孔体积。
10.如权利要求1所述的催化剂,其中所述基础挤出物具有0.02至0.35cc/g的在20-50nm孔径范围内的孔体积,或0.03至0.30cc/g的在20-50nm孔径范围内的孔体积,或0.05至0.25cc/g的在20-50nm孔径范围内的孔体积。
11.如权利要求1所述的催化剂,其中所述基础挤出物具有0.20至1.65cc/g的在2-50nm孔径范围内的总孔体积,或0.25至1.50cc/g的在2-50nm孔径范围内的总孔体积。
12.如权利要求1所述的催化剂,其中所述SSZ-91分子筛包含ZSM-48型沸石材料,所述分子筛具有:
所述总ZSM-48型材料的至少70%多型体6;
0重量%与3.5重量%之间的量的EUO型相;以及
多晶聚集体形态,所述多晶聚集体形态包含具有在1与8之间的平均纵横比的微晶。
13.如权利要求1所述的催化剂,其中所述改性剂含量为0.01-5.0重量%或0.01-2.0重量%或0.1-2.0重量%(基于总催化剂重量)。
14.如权利要求1所述的催化剂,其中所述催化剂包含0.01-1.0重量%或0.3-0.8重量%Pt的量的Pt作为改性剂。
15.如权利要求1所述的催化剂,其中所述分子筛的氧化硅与氧化铝的摩尔比在40-220或50-220或40-200或50-140的范围内。
16.如权利要求1所述的催化剂,其中所述SSZ-91分子筛包含以下中的一者或多者:
所述总ZSM-48型材料的至少80%或90%多型体6;
0.1重量%与2重量%之间的EU-1;
具有在1与5之间,或在1与3之间的平均纵横比的微晶;
或它们的组合。
17.如权利要求1所述的催化剂,其中所述催化剂进一步包含选自氧化铝、二氧化硅、二氧化铈、二氧化钛、氧化钨、氧化锆或它们的组合的基质材料。
18.如权利要求17所述的催化剂,其中所述催化剂包含0.01重量%至5.0重量%的所述改性剂、0重量%至99重量%的所述基质材料和0.1重量%至99重量%的所述SSZ-91分子筛,或其中所述催化剂包含0.01重量%至5.0重量%的所述改性剂、15重量%至85重量%的所述基质材料和15重量%至85重量%的所述SSZ-91分子筛。
19.如权利要求18所述的催化剂,其中所述基质材料包含15重量%至65重量%的第一基质材料和15重量%至65重量%的不同于所述第一基质材料的第二基质材料。
20.一种用于生产具有增加的基础油产物产率的基础油产物的工艺,所述工艺包括使烃进料与权利要求1所述的加氢异构化催化剂在加氢异构化条件下接触以生产基础油产物。
21.如权利要求20所述的工艺,其中所述烃进料包含瓦斯油;真空瓦斯油;久沸残渣;真空残渣;常压馏出物;重质燃料;油;蜡和石蜡;用过的油;脱沥青残渣或原油;由热转化或催化转化过程产生的装料;页岩油;循环油;动物和植物来源的脂肪、油和蜡;石油和疏松蜡;或它们的组合。
22.如权利要求20所述的工艺,其中使用权利要求1所述的催化剂时的所述基础油产率与使用对比加氢异构化催化剂的相同工艺相比有所增加,所述对比加氢异构化催化剂的不同之处仅在于所述氧化铝组分不具有0.05至1.0cc/g,或0.07至0.85cc/g,或0.09至0.70cc/g的在11-20nm孔径范围内的孔体积。
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CA2046279C (en) | 1989-02-17 | 2001-01-02 | Stephen J. Miller | Isomerization of waxy lube oils and petroleum waxes using a silicoaluminophosphate molecular sieve catalyst |
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US8790507B2 (en) | 2010-06-29 | 2014-07-29 | Chevron U.S.A. Inc. | Catalytic processes and systems for base oil production using zeolite SSZ-32x |
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US9802830B2 (en) | 2015-08-27 | 2017-10-31 | Chevron U.S.A. Inc. | Molecular sieve SSZ-91 |
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