CN106163655A - 用于原料热解的催化剂 - Google Patents
用于原料热解的催化剂 Download PDFInfo
- Publication number
- CN106163655A CN106163655A CN201580018022.3A CN201580018022A CN106163655A CN 106163655 A CN106163655 A CN 106163655A CN 201580018022 A CN201580018022 A CN 201580018022A CN 106163655 A CN106163655 A CN 106163655A
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- Prior art keywords
- catalyst
- raw material
- mixture
- weight
- zeolite
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 254
- 239000002994 raw material Substances 0.000 title claims abstract description 65
- 238000000197 pyrolysis Methods 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 86
- 238000005336 cracking Methods 0.000 claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 239000010457 zeolite Substances 0.000 claims description 75
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 74
- 229910021536 Zeolite Inorganic materials 0.000 claims description 71
- 239000007789 gas Substances 0.000 claims description 49
- 239000004005 microsphere Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 229920005610 lignin Polymers 0.000 claims description 20
- 239000002028 Biomass Substances 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- -1 oxybenzene compound Chemical class 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052702 rhenium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- CHWNEIVBYREQRF-UHFFFAOYSA-N 4-Ethyl-2-methoxyphenol Chemical compound CCC1=CC=C(O)C(OC)=C1 CHWNEIVBYREQRF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229960001867 guaiacol Drugs 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 2
- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical class N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 claims description 2
- 241000269350 Anura Species 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 41
- 239000003795 chemical substances by application Substances 0.000 abstract description 25
- 239000002904 solvent Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 60
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- 239000002253 acid Substances 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000000571 coke Substances 0.000 description 19
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 239000005995 Aluminium silicate Substances 0.000 description 10
- 235000012211 aluminium silicate Nutrition 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229960004424 carbon dioxide Drugs 0.000 description 9
- 239000004927 clay Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 150000001491 aromatic compounds Chemical class 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 229910002090 carbon oxide Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003863 metallic catalyst Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
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- 230000008859 change Effects 0.000 description 5
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- 238000006297 dehydration reaction Methods 0.000 description 5
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- 229910052733 gallium Inorganic materials 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
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- 238000001694 spray drying Methods 0.000 description 4
- 229910019020 PtO2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 229910019571 Re2O7 Inorganic materials 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- ORVGYTXFUWTWDM-UHFFFAOYSA-N silicic acid;sodium Chemical compound [Na].O[Si](O)(O)O ORVGYTXFUWTWDM-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
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Abstract
本发明提供了用于在单阶段中将原料加工成单芳香族化合物的新型催化剂混合物,所述催化剂混合物包括至少一种裂化催化剂、一种多相过渡金属催化剂和任选的至少一种氢化催化剂。该过程在一步或单阶段中发生,基本上无溶剂或外部添加剂,或当原料含有小于15%氧时,该过程包括另外的水或蒸汽以允许原位产生足够量的H2。
Description
技术领域
本发明涉及使用新型催化剂混合物的原料单阶段催化性快速热解(“CFP”)。
背景技术
在由生物来源的废弃材料或含聚合物原料生产液体燃料和化学前体中目前存在相当大的兴趣。
木质纤维素生物质作为用于生产可再生液体生物燃料和其他商业上有价值的化合物的原料是特别感兴趣的。它是木本植物和非木本植物的主要结构组分,并且由纤维素、半纤维素和木质素组成。在木质纤维素生物质(主要是木质素)中发现的芳香族碳水化合物聚合物对于生产高价值平台化学品是感兴趣的,所述平台化学品包括单芳香族化合物例如苯、甲苯、二甲苯、己内酰胺、苯酚及其衍生物(例如,愈创木酚和儿茶酚),所述平台化学品可用于制备各种化学品和材料。平台化学品是对于溶剂、燃料、聚合物、药物、香料和食物的重要前体。
木质纤维素生物质或生物来源的原料通过热解的转换涉及许多反应步骤,从而导致含有多重组分以及显著水蒸气、二氧化碳和焦炭的液体产物。转换过程可为非催化的,但催化通过去除液体产物中的氧,增加H:C比,并且增加总体得率,来改善液体产物的质量。用于将固体生物质转换为液体组分例如燃料的目前方法涉及多个步骤和长加工时间,这极大增加了生物质加工的成本。已作为实现此类目标的可行技术出现的一个过程是快速热解。快速热解通过在高温下在短时间量中的还原转换,将许多生物来源的材料转换为液体烃。
设想小转换工厂可定位接近于大型生物质源,并且将材料转换为液体形式,所述液体形式可使用现有基础设施容易地运输至炼油厂和化工厂,以在常规烃加工设备中进行(共)加工。为了实现这种愿景,所产生的液体产物必须具有允许类似于化石烃加工的特性,并且衍生的液体和产物的价值必须足以抵消生物质加工步骤的附加成本。为此,认识到需要催化剂以便调谐产物的特性和得率。被催化的过程通常被称为催化性快速热解(CFP)。
CFP采用在沸石催化剂的存在下,在非氧化大气中生物质快速加热至在400℃至600℃范围内的温度,并且在单一步骤中将生物质转换为汽油相容性芳香族化合物。尽管CFP需要较短的停留时间且使用廉价催化剂,但一般而言,木质素及其他生物质组分经由CFP转换为液体烃具有高焦炭得率和酸性液体产物的缺点,所述酸性液体产物具有剩下的高级分的氧。此外,CFP产生大量CO和CO2以及蒸汽。所有这些观察结果的原因可追溯到进料的氧含量和经过常规解聚催化剂发生的反应类型。与烃不同,碳水化合物的裂化导致高度反应性含氧化合物的形成。这些含氧化合物趋于与其他含氧部分或烯烃缩合,以形成焦炭。任何剩余含氧化合物均促成最终产物的酸度,并且反应器中氧的存在导致CO、CO2和蒸汽的形成。因此,用于木质素CFP的催化剂必须考虑这些附加反应进行设计。通常,生物质的加工还可在两步过程中完成,其中在500℃-700℃下的快速热解随后为在约400℃下的催化热解。两步过程增加液体的得率,但在经济上不可行。此外,期望使用除原材料外的最低限度外部添加剂或不使用外部添加剂例如气体或液体,以减少CPF过程中的操作和材料成本。
多步CPF和/或利用添加剂的CPF是工业中众所周知的。例如,给予Chen的美国专利公开号2013/0030228教导了产生含芳香族烃的流出物的方法,所述方法包括在催化剂、氢和有机溶剂的存在下快速加热基于生物质的原料的步骤,以形成含芳香族烃的流出物。
给予Huber的美国专利公开号2009/0227823教导了经由催化热解用于流体烃产物的组合物和方法,所述催化热解涉及使用包括固体含烃材料和多相热解催化剂组分的混合物的组合物。
给予Huber的美国专利公开号2013/0060070教导了用于由固体含烃材料产生一种或多种流体烃产物的方法,所述方法包括:将固体含烃材料和氢或氢源进料至反应器,随后使固体含烃材料热解,并且使热解产物和氢催化反应,以产生一种或多种流体烃产物。
给予Sarkar的美国专利号8,487,142教导了用于由含碳材料产生小分子量有机化合物的过程,所述过程包括在预定温度和压力下,在变换催化剂的存在下,使含碳材料与一氧化碳(CO)和蒸汽接触的步骤。
给予Chen的美国专利号8,404,908教导了包括在氢大气下,使木质素与氢化催化剂反应,以将酸性含氧化合物转换为较少酸性的含氧化合物或烃的过程。含氧化合物在脱氢和脱氧过程中反应,以去除氧,并且将环状烃转换回芳香族化合物。
上述现有技术教导了多步或多阶段过程,或外部添加剂例如溶剂和/或气体的添加,以起始含碳材料的解聚过程。因此,存在对使用具有最低限度的添加剂或不含添加剂的催化剂组合物的单阶段、一锅法的需要,以由聚合物产生液体解聚产物,例如由木质素和木质纤维素原料产生单芳香族化合物,伴随改善的得率、减少的焦炭产生和一氧化碳的管理。还存在对催化剂组合物的需要,通过在单一组合物中掺入多重催化官能团,所述催化剂组合物提供了经济上更可行的过程,由此减少所需过程步骤数目。
发明内容
本发明涉及用于原料的单阶段催化性快速热解(“CFP”)的新型催化剂混合物,所述催化剂混合物包括:1)至少一种裂化催化剂;2)多相过渡金属水-煤气变换催化剂;和任选的3)至少一种氢化催化剂。本发明还涉及使用新型催化剂混合物的原料的单阶段催化性快速热解,以产生单芳香族化合物产物,基本上无溶剂或其他外部添加剂。可替代地,对于含有小于15%氧的原料,本发明还涉及使用新型催化剂混合物的单阶段催化性快速热解,伴随另外的水或蒸汽,以产生单芳香族化合物。
与本领域已知的常规催化剂相比较,新型催化剂混合物产生格外高量的单芳香族化合物,所述单芳香族化合物是用于下游商业产物的有用中间产物。
附图说明
为了本发明的性质和优点的更完全理解,应参考与附图结合阅读的下述详述。
图1示出了使用新型催化剂混合物,使芳香族聚合物催化性快速热解为单芳香族化合物的步骤,所述新型催化剂混合物执行(perfume)催化裂化、水-煤气变换和任选的氢化。
具体实施方式
本发明涉及用于原料的单阶段催化性快速热解(“CFP”)的新型催化剂混合物,所述催化剂混合物包括:1)至少一种沸石裂化催化剂;2)多相过渡金属水-煤气变换催化剂;和任选的3)至少一种氢化催化剂。本发明还涉及评价原料的氧含量,使得在大于15重量%的氧含量下,原料经历使用新型催化剂混合物的单阶段催化性快速热解,以产生单芳香族化合物产物,基本上无溶剂或其他外部添加剂。可替代地,对于具有小于15重量%氧含量的原料,原料经历使用新型催化剂混合物和另外的水或蒸汽的单阶段CFP,以确保原位产生足够量的氢气用于氢化。
与本领域已知的常规催化剂相比较,新型催化剂混合物产生格外高量的单芳香族化合物,所述单芳香族化合物是用于下游商业产物的有用中间产物。
术语“原料”和“生物质原料”指基于植物的原始材料,其含有高分子量和高沸点的芳香族CHO聚合物。在该定义内包括的是“木质纤维素生物质”,其指由碳水化合物聚合物(例如纤维素、半纤维素)和芳香族聚合物木质素组成的植物物质。碳水化合物聚合物通常与木质纤维素生物质中的木质素结合。木质纤维素是用于本发明的方法的合适原料或底物,其中高分子量芳香族CHO聚合物解聚且转换为更有价值的单芳香族化合物产物。替代的合适原料包括含有基于植物的材料,但并非直接得自植物的任何材料,例如粪便、市政废物(如食物废物或污水)和得自植物材料中的纤维素的酶促加工的生物质。
术语“解聚产物”指通过原料内的聚合物解聚产生的单体或寡聚体的化合物。这些产物具有比它们来源于其的聚合物更低的分子量,并且包括可用作平台化学品、合成气和合成油的化合物。由于其减少的分子量,这些产物是液体,而它们通过解聚来源于其的聚合物是固体。
短语“反应性单芳香族化合物”及其等价物指来源于下述的单芳香族化合物:1)含芳香族CHO聚合物原料的解聚,和2)通过解聚产生的解聚产物的脱羰、脱羧和/或脱水。
术语“单芳香族化合物(monoaromatic)”、“单芳香族化合物(monoaromaticcompound)”和“单芳香族化合物产物”可互换使用,并且指的是在本文的CFP过程中来源于反应性单芳香族化合物的终产物单体。这些产物是苄基化合物、苯酚化合物及其衍生物例如2-甲氧基-苯酚、1,2-苯二酚、4-乙基-2-甲氧基-苯酚、2-甲氧基-6-甲基苯酚、2-甲氧基-4-(1-丙烯基)-苯酚、苯酚、2-甲氧基-4-丙基-苯酚、乙酮、1-(4-羟基-3-甲氧基苯基)-苯酚、3-甲基-苯酚、2-甲氧基-4-甲基苯酚。单芳香族化合物的特征在于小于220℃的沸点。
术语“微球体”指一般通过喷雾干燥形成的小孔颗粒。如技术人员理解的,微球体在形状中不一定是完全球形的。微球体具有在微米(micrometer)或微米(micron)范围内(约1-999μm)的直径。
术语“基体组分”指微球体的结构载体组分,所述结构载体组分一般是相对惰性的材料(即并非催化活性组分)。例如,基体组分可选自高岭石、埃洛石、蒙脱石、膨润土、绿坡缕石、高岭土、无定形高岭土、偏高岭土、莫来石、尖晶石、水合高岭土、粘土、三水铝石(三水氧化铝)、勃姆石、二氧化钛、氧化铝、二氧化硅、二氧化硅-氧化铝、二氧化硅-氧化镁、氧化镁和海泡石。
术语“原位结晶”指这样的过程,其中沸石在微球体上/在微球体中直接生长或共生,并且与基体组分紧密结合,如美国专利号4,493,902和6,656,347中所述。用于制备携带一种或多种原位结晶沸石的多孔微球体的一种合适方法在美国专利号6,716,338中描述。
短语“基本上无溶剂或其他外部添加剂”等价于“基本上不含溶剂或其他外部添加剂”,指小于5%、优选小于1%、且更优选小于0.5%的原料和新型催化剂混合物的总反应混合物,使得添加剂对CFP和单芳香族化合物的后续生产不促成显著作用。
裂化催化剂
对于本发明有用的裂化催化剂是这样的催化剂,所述催化剂促进芳香族CHO聚合物的含共价氧的键的破坏(即解聚或“裂化”),以产生更小的芳香族CHO聚合物(包括二聚体和三聚体)和寡聚物。适用于本发明的解聚或裂化催化剂包括但不限于沸石催化剂以及非沸石催化剂(例如分子筛、固体酸催化剂、WOx/ZrOz、氧化铝、磷酸盐等)。
对于催化性快速热解过程(“CFP”),特别有利的裂化催化剂可包括含有根据孔径(例如通常与沸石相关的中孔和孔径)选择的内部孔隙率的那些,例如小于约100埃、小于约50埃、小于约20埃、小于约10埃、小于约5埃或更小的平均孔径。在一些实施例中,可使用具有约5埃至约100埃的平均孔径的催化剂。在一些实施例中,可使用具有约5.5埃至约6.5埃、或约5.9埃至约6.3埃的平均孔径的催化剂。在一些情况下,可使用具有约7埃至约8埃、或约7.2埃至约7.8埃的平均孔径的催化剂。
在CFP的一些实施例中,沸石催化剂可选自天然存在的沸石、合成沸石及其组合。催化剂可为ZSM-5沸石催化剂。催化剂可包括酸性位点。可使用的其他沸石催化剂可包括镁碱沸石、沸石β、Y型沸石、丝光沸石、MCM-22、ZSM-23、ZSM-57、SUZ-4、EU-1、ZSM-11、(S)A1P0-31、SSZ-23、SAPO、ALPA、MeALPO等等。
在某些实施例中,可使用包含镓的Mordenite Framework Inverted(MFI)沸石催化剂。例如,可使用镓硅铝酸盐MFI(GaAlMFI)沸石催化剂。本领域普通技术人员将熟悉GaAlMFI沸石,其可被认为是其中一些Al原子已替换为Ga原子的硅铝酸盐MFI沸石。在一些情况下,沸石催化剂可采取氢的形式(例如H--GaAlMFI)。镓硅铝酸盐MFI催化剂可为ZSM-5沸石催化剂,其中在一些实施例中,一些铝原子已替换为镓原子。
筛选方法可用于选择具有适当孔径的催化剂用于特异性热解产物分子的转换。筛选方法可包括测定需要被催化反应的热解产物分子的大小(例如热解产物分子的分子动力学直径)。本领域普通技术人员可例如计算给定分子的动力学直径。催化剂类型随后可这样加以选择,使得催化剂的孔(例如诺曼调整的最小半径)足够大,以允许热解产物分子扩散到催化剂内和/或与催化剂反应。在一些实施例中,催化剂加以选择,以使得其孔径足够小以阻止热解产物的进入和/或热解产物的反应,所述热解产物的反应将是不期望的。
在一些实施例中,可能期望采用一种或多种催化剂以确定孔径的双峰分布。在一些情况下,可使用具有孔径的双峰分布的单一催化剂(例如主要包含5.9-6.3埃孔和7-8埃孔的单一催化剂)。在其他情况下,两种或更多种催化剂的混合物可用于确定双峰分布(例如两种催化剂的混合物,每种催化剂类型包括不同范围的平均孔径)。
本发明的沸石裂化催化剂优选包括大孔催化剂(由12元环组成)和小孔或中等孔沸石(由8-10元环组成)中的至少一种。例子包括高基体Y型沸石和ZSM-5。Y型沸石具有通过12元环形成的大孔(约孔径),并且有助于高分子量木质素原料的解聚/裂化。ZSM-5是具有通过5元环形成的小至中等线性孔(大约直径)的五元环沸石,其为裂化或解聚催化剂,但还可提供用于由烯烃产生单芳香族化合物的选择性,所述烯烃作为在热解期间的中间产物产生。
其他大孔沸石催化剂同样适用于本发明中用于解聚,例如12元环沸石包括骨架型FAU、CHA、MOR等等。Y型沸石包括在该组中。由8-10元环组成的其他小孔/中等孔沸石催化剂包括骨架型ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、TH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON、MFI、LTA、BEA等等,并且这些同样适用于本发明中用于解聚和单芳香族化合物选择性。具体例子包括例如ZSM-11、MFI沸石和MCM。如果至少一种大孔沸石和至少一种小沸石的混合物一起掺入以形成沸石催化剂,则沸石催化剂优选具有基于沸石催化剂的总重量,10:1至1:10、优选5:1至1:5、且更优选3:1至1:3的大沸石与小沸石比率。
裂化催化剂负载于固体载体上。固体载体可采取多孔微球体的形式,以提供用于催化反应的增加的表面积。微球体的孔通常这样选择,以使得它们足够大以允许被原料中的大聚合物例如芳香族CHO聚合物进入。解聚催化剂可掺入微球体内,或在微球体内原位形成。在某些具体实施例中,解聚催化剂(例如Y型沸石)在微球体的孔内原位结晶。在某些具体实施例中,多孔微球体为直径约70-90μm,或直径约80μm。在进一步的具体实施例中,多孔微球体具有在直径约90-110nm范围内、或直径约100nm的大多数孔。具有原位结晶的沸石的合适微球体可如美国专利4,493,902中所述产生,所述美国专利以引用的方式并入本文。
水-煤气变换催化剂
催化剂混合物还包括多相过渡金属水-煤气变换催化剂。水-煤气变换催化剂由在木质素或原料热解期间产生的水蒸气和一氧化碳生成原位氢分压。原位分压氢与反应性单芳香族化合物反应,伴随或不伴随氢化催化剂的存在,以产生终产物单芳香族化合物。
多相过渡金属催化剂包含在载体上的至少一种金属催化剂,所述载体任选通过金属酸促进剂得到促进。金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡、铁、锌、金、银或其混合物。载体选自锆、二氧化硅、Al2O3(氧化铝)、TiO2及其混合物。载体是任选通过酸促进剂促进的酸,所述酸促进剂选自钨、铌、钼、铈、锰、钒、铼和钽。
优选地,金属催化剂选自铂、钯、钌、铼、铑及其混合物。金属催化剂可促成CFP过程中的氢化、氢解、脱羰和脱羧。水-煤气变换催化剂中的金属催化剂或金属催化剂混合物的量为按重量计约0.01%至约20%;优选约0.5%至约10%;更优选约0.5%至约5%;最优选按重量计0.5%至约2%,或按重量计约0.5%至约1%也是有用的。更优选地,多相水-煤气变换催化剂含有在促进的载体上的至少一种金属或金属氧化物、在任选促进的载体上的至少两种金属或金属氧化物。
至少一种金属催化剂负载于锆、二氧化硅、Al2O3、TiO2或其混合物上。载体任选通过金属酸促进剂得到促进,所述金属酸促进剂可促成CFP过程中的脱水、水解或两者。酸促进剂可增加载体的酸度且产生另外的酸位点。在一个实施例中,酸促进剂选自钨、铌、钼、铈、锰、钒、铼和钽。酸促进剂可为超过一种金属的组合。在另一个实施例中,酸促进剂选自钨、铌和钼。在另一个实施例中,酸促进剂是钼。在一个实施例中,酸促进剂的量可为按载体的重量计约0.01%至约99%。在另一个实施例中,酸促进剂的量可为按载体的重量计0.1%至约50%;约0.5%至约25%;约1%至约15%;或约5%至约10%。
酸促进剂通常通过初湿浸渍法或浸渍法加入载体中,所述加入随后为活性金属的添加。载体在此处通常指具有1.5磅/mm以上的抗碎强度的成形载体。酸促进剂溶解于溶剂通常为水中,并且通过初湿浸渍或浸渍法或将促进剂有效分散到载体内的任何其他方法加入载体中。混合物随后干燥且随后为在高温下的煅烧。该过程可重复以将另外的酸促进剂加入载体中。在另一个实施例中,在挤出和煅烧之前,通过将促进剂与载体物理混合来添加酸促进剂。在另一个实施例中,酸促进剂通过下述进行添加:用碱沉淀到载体浆料内,随后为过滤、干燥、挤出、煅烧。酸促进剂前体是水溶性盐、金属氧化物、金属氢氧化物。在一个实施例中,酸促进剂前体是铌酸铵草酸盐、偏钨酸铵水合物、钼酸铵四水合物、钼酸钠盐脱水物、铌酸和钨酸。
改变酸促进剂、量和煅烧温度和/或酸促进剂的组合将改变催化剂载体的酸位点数目和酸强度。
水-煤气变换催化剂可通过经由常规初湿浸渍法、或浸渍法、或将方法有效分散到载体上的任何其他方法,通过将金属催化剂前体加入任选促进的载体形成。初湿浸渍法涉及将催化剂前体溶液滴到载体(earner)上,直至完全湿润载体,随后为干燥和煅烧。换言之,消耗的前体溶液体积等于载体的总孔体积。为了实现所需负荷,上述程序可重复几次。浸渍法涉及伴随热和搅拌,将载体置于含有过量溶解的催化剂前体的溶液中。载体从溶液中取出且随后干燥且煅烧。在一个实施例中,在加入载体之前,使金属催化剂前体溶解于溶剂(一个例子是水)中。使湿润材料干燥,随后为以控制速率加热至约450℃的温度用于煅烧材料。
优选地,水-煤气变换催化剂包含选自铂、铼、铁、钴及其混合物的至少两种金属氧化物;选自Al2O3和二氧化硅的载体,其中所述载体通过铈、钼和钨得到促进。更优选地,过渡金属水-煤气变换催化剂包含铂和铼的混合物,以及通过钼促进的Al2O3载体。
氢化催化剂
氢化催化剂使来源于木质素的反应性单芳香族化合物氢化,然后它们能够缩合且再聚合为焦炭。在一个或多个实施例中,氢化催化剂可为由Al2O3、二氧化硅或其他惰性基体负载的碱金属或碱金属氧化物。在进一步的具体实施例中,碱金属或碱金属氧化物选自镍(Ni)、铜(Cu)、锌(Zn)及其组合,其中碱金属为30-90重量%、优选50-85重量%、且更优选60-80重量%的氢化催化剂。优选地,氢化催化剂是Ni的氧化物。
必须指出本发明的催化剂混合物任选包括氢化催化剂。氢化催化剂是任选的,因为氢化仍可伴随反应性单芳香族化合物而原位发生,伴随通过水-煤气变换催化剂生成的氢气的存在。
在前述实施例的任一个中,催化剂混合物包含基于催化剂混合物的总重量,约20-90重量%、优选约40-85重量%、且最优选约50-80重量%的裂化催化剂;约3-80重量%、优选约5-40重量%、且最优选约7-20重量%的多相过渡金属水-煤气变换催化剂;和任选的约3-20重量%、优选5-15重量%、且最优选7-10重量%的氢化催化剂。还应理解因为沸石在过程中随着时间过去经历分解,因此当沸石用作裂化催化剂时,可能期望增加本发明的催化剂混合物中的沸石催化剂的量,以补偿且提供更久的有用的催化寿命。例如,在某些情况下,沸石裂化催化剂可以约40-90重量%的量存在于催化剂组合物中。总之,催化剂混合物包含基于催化剂混合物的总重量,沸石裂化催化剂内的总共约25-90重量%、优选35-85重量%、且更优选40-80重量%的沸石;约7-10重量%、优选7.5重量%的包含Mo促进的Pt和Re氧化物的水-煤气变换催化剂(例如5.6重量%Pt氧化物和3重量%Re氧化物);和任选约7-10重量%、优选7.5重量%的包含NiO的氢化催化剂。具体地,水-煤气变换催化剂含有6.61%PtO2、3.88%Re2O7和0.715%MoO3。在另一个实施例中,组分的总体浓度为最终催化剂混合物中的0.5%PtO2、0.3%Re2O7、0.05%MoO3和5.5%NiO。各种催化剂以所需比例作为微粒或粉末组分混合在一起。
生产方法
裂化或解聚催化剂、水-煤气变换催化剂和任选的氢化催化剂可掺入多孔微球体内或多孔微球体上,所述多孔微球体一般包含惰性基体材料例如煅烧高岭土粘土。在催化剂组合物中可使用的其他惰性组分包括另外的粘土、粘合剂等等。在一个或多个实施例中,催化剂混合物的至少一种沸石可采取在微球体的孔中原位结晶的沸石的形式,所述微球体包含惰性基体例如煅烧高岭土粘土。
具有有效直径大于约的孔开口的大孔沸石裂化催化剂特别可用于在微球体的孔内的原位结晶,因为它们对于大聚合物的解聚是选择性的。此类大孔沸石的例子包括沸石X;REX;Y型沸石;超稳Y(USY);稀土交换的Y(REY);稀土交换的USY(REUSY);脱铝Y(DeAlY);超疏水性Y(UHPY);和/或脱铝富含硅的沸石例如LZ-210。大孔沸石可如上所述原位结晶,或它可通过喷雾干燥制备成微粒制剂,所述微粒制剂在催化剂混合物中混合。具有更小有效直径的孔且对于由解聚过程中产生的烯烃生产更小的单芳香族化合物选择性的至少第二沸石的添加,在催化剂混合物中也是有用的。合适的小孔沸石的一个例子是ZSM-5,其具有八环线性孔构型。此类小孔/中等孔沸石的其他合适例子包括ZSM-11、MFI沸石和MCM。小孔沸石可在煅烧粘土微球体中原位结晶,但也可喷雾干燥成在多功能催化剂组合物中混合的微粒制剂。
可替代地,沸石掺入微球体上涉及:使沸石结晶且随后在浆料中与粘土、粘合剂、氧化铝等组合且喷雾干燥,以形成活性微球体。后处理如交换和煅烧将类似于原位方法应用。
在本文描述的多功能催化剂组合物的任一种中有用的微球体颗粒的例子在美国专利号6,716,338中描述,所述美国专利以引用的方式并入本文。这些微球体最初包括水合高岭土粘土和/或偏高岭土,任选的可分散的勃姆石、任选的尖晶石和/或莫来石、以及硅酸钠或硅溶胶粘合剂作为基体组分,但随后煅烧以将水合高岭土转换为偏高岭土,并且将勃姆石转换为过渡型氧化铝。在本发明中有用的沸石催化剂中的任一种可以这种方式进行制备。需要时,沸石裂化催化剂随后可通过与碱性硅酸钠溶液反应和离子交换,以所需量在微球体的孔中原位结晶。
使用方法(CFP)
本发明的实施例还提供了用于由含氧聚合物原料(例如来自含芳香族CHO聚合物原料的单芳香族化合物)生产液体解聚产物的方法,其中使用上文描述的整合的多功能催化剂组合物中的任一种。在某些实施例中,原料具有按重量计至少15%、例如按重量计约15-50%或按重量计约15-30%的氧含量。含芳香族CHO聚合物原料可包括木质素。本发明的方法可用于从含芳香族CHO聚合物原料中分离单芳香族化合物,包括例如苄基化合物和苯酚化合物,并且能够将至少15重量%的原料进料转换为单芳香族化合物。
在一个或多个实施例中,用于由含氧聚合物原料生产解聚产物或单芳香族化合物的方法包括下述:a)评价原料的氧含量;b)对于具有至少15%的氧含量的原料,使包含含氧聚合物的原料与催化剂混合物反应,所述催化剂混合物包括至少一种裂化或解聚催化剂、多相过渡金属水-煤气变换催化剂和任选的至少一种氢化催化剂,其中所述反应混合物基本上不包括溶剂或其他外部添加剂;可替代地,对于含有小于15%氧含量的原料,将另外的水或蒸汽加入反应混合物中,使得新型催化剂混合物使原料裂化,从而将在解聚期间产生的一氧化碳(CO)和水(H2O)转换为氢(H2)以及氢化反应性单体和中间产物(例如反应性单芳香族化合物),以产生液体解聚产物(例如单芳香族化合物);和c)回收液体解聚产物的化合物。
产生本发明的单芳香族化合物的方法还包括评价原料的氧含量的手段,以及将适当量的水或蒸汽分配到原料/催化剂混合物反应混合物内的手段,以确保原位产生足够量的氢用于氢化。需要时,水或蒸汽优选用提升气体分配到反应器内。具体地,蒸汽含量通过对于每个裂化实验的持续时间以0.1ml/分钟添加水加以控制,以确保原位产生足够量的氢气用于氢化反应。
在某些实施例中,用于解聚、水-煤气变换和氢化反应的操作温度为约350℃至600℃、约400至500℃、或约350至450℃。优选地,用于解聚、水-煤气变换和氢化反应的操作温度为约400至500℃。尽管该过程可在升高的压力下执行,但使用催化剂混合物的特别优点在于该过程在低压例如大气压或约1-2atm下有效进行。优选地,本发明的CFP过程在15分钟内、更优选在10分钟内、且最优选在5分钟内完成。
用于由含芳香族CHO聚合物原料产生单芳香族化合物的过程的理论化学再次在图1中示出。在第一步中,催化剂混合物的芳香族CHO聚合物解聚催化剂组分“裂化”原料中含有的芳香族CHO聚合物(即木质素),以产生单芳香族化合物、寡聚物或更短的聚合物化合物例如二聚体和三聚体、烯烃、CO和水的混合物。当存在对于由烯烃生产单芳香族化合物选择性的第二芳香族CHO聚合物解聚催化剂例如ZSM-5沸石时,烯烃转换为单芳香族化合物而不是缩合为焦炭。最初通过裂化产生的单芳香族化合物的脱羰、脱羧和脱水导致能够再形成二聚体和三聚体芳香族化合物的反应性单芳香族化合物。
根据下述反应,水-煤气变换催化剂将在解聚步骤期间产生的一氧化碳和水转换为氢:
使用同时发生的WGS反应中产生的氢的这些反应性单芳香族化合物的氢化使其稳定,阻止再聚合,且产生最终的单芳香族化合物产物,所述产物可使用本领域已知的技术进行回收。如图1中所示的反应步骤连续(即同时)且在相同反应器中发生,而无需任何另外的溶剂或气体以起始解聚。图1还示出了裂化过程的副反应,其中裂化过程的产物的缩合再缩合以产生焦炭。焦炭是不期望的反应产物,在商业催化性裂化过程中催化剂的高度放热再生期间,所述反应产物引起通过烧掉焦炭生成的热中的增加。导致对焦炭的高水平转换的催化剂在商业过程中具有有限效用,即使它们是高度催化活性的。
用于由含聚合物原料中的含氧聚合物产生液体解聚产物的过程的第一步通常涉及以所需催化剂:进料比混合原料和催化剂混合物。催化剂:进料的比例一般基于原料中存在的含氧聚合物的量加以选择。在某些实施例中,催化剂混合物与含氧聚合物的比率为按重量计约2-10:1、按重量计约4-9:1、按重量计约9:1或按重量计约5:1。混合物随后置于在约400℃下的反应器中用于热解,且在催化反应期间保持在该温度下。使液体产物冷凝且收集。具有小于220℃的沸点的产物是所需单芳香族化合物。
在用于由含芳香族CHO聚合物原料产生单芳香族化合物的前述方法的任一种中,原料可源自任何含芳香族CHO聚合物材料,例如原始生物质(树木、灌木和草)、农业残余(例如玉米秸秆或穗、稻草、甘蔗渣等)、经加工的生物质的团块、木片和木材残余(例如来自锯木厂和制浆工艺的废物)、以及作为生物燃料生产的原始材料而生产的能源作物(例如柳枝稷或象草)。优选地,由原料中含有的木质素产生单芳香族化合物。
另外,在用于由原料中的含氧聚合物产生液体解聚产物的前述方法的任一种中,原料还可包含聚合物例如聚苯基醚(PPE)、聚苯撑醚(PPO)、聚甲醛(POM)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚四氢呋喃(PTHF)、和/或聚碳酸酯和聚酯(包括脂肪族、半芳香族和芳香族变体)。
在前述方法的某些实施例中,用于原料的单阶段转换的过程在类似于用于加工石油的FCC过程的循环流化床催化裂化(FCC)***中实现;然而,应认识到与石油加工不同,本文过程中的原料是固体而不是液体。原料中存在的含氧聚合物例如木质素具有与石油的一些共同特征。例如,它们是具有高芳香族含量的高分子量聚合物,所述高芳香族含量难以化学加工。本发明的催化剂混合物使得能够使聚合物解聚和木质素生物加工适合商业上使用的用于加工石油的FCC***。
在本发明的CFP过程中,热整合的催化剂混合物作为粉末或微粒材料加入,悬浮于含氧聚合物原料中,并且在FCC单元的提升管部分中向上推进到反应区内,原料在所述反应区中在高温下裂化。提升气体例如氮与催化剂混合,以提供流态化悬浮液。反应产物和耗尽的催化剂随后从提升管排放到分离器内,在所述分离器中反应产物输送至回收区,并且催化剂送往催化剂再生器单元。流态化催化剂在提升管和再生器之间连续循环,以供应用于裂化反应的热,且将进料维持在所需反应温度下。优选地,在本发明的CFP过程中,因为流态化催化剂混合物和进料在反应器中向上定向,所以进料中的含氧聚合物解聚,并且同时发生的反应性液体解聚产物(反应性单芳香族化合物)产生且氢化为最终稳定的单芳香族化合物产物。还同时发生的是,在解聚期间产生的CO在水的存在下通过水-煤气变换催化剂转换为CO2和H2,并且原位H2用于氢化中。
由于热解,焦炭在催化剂上沉积,而催化反应的更轻、更有价值的产物(包括单体、二聚体、三聚体和寡聚物)离开提升管,并且进入在反应容器顶部处的固体-气体分离***,它们在所述反应容器中分级以分离且回收稳定的单芳香族化合物。将焦炭化催化剂导向催化剂再生区,焦炭在所述催化剂再生区中通常在600℃至850℃的温度下被烧掉,并且随后将催化剂再循环回到FCC单元的提升管部分内,用于单芳香族化合物的连续生产。
本发明的CFP过程将至少15重量%、优选至少40重量%、且更优选至少60重量%的原料转换为单芳香族化合物产物。
与使用单独的沸石相比较,本发明的催化剂混合物提供了单体的更高产生以及减少量的二聚体、三聚体和寡聚物。还存在与单独的沸石相比较焦炭生产中的减少,其导致改善的催化剂再生和效用。本发明的催化剂混合物的进一步优点涉及同时执行反应过程的所有步骤的能力,与序贯相反,单阶段在一个反应器中,因此提供可适合商业生产过程例如FCC的连续过程。此类同时过程不仅消除序贯过程步骤,直接由原料原位生产氢还消除关于分开的外部氢输入的需要,用于维持最终产物中可接受的H:C比,并且改善此类过程的总体氢管理。考虑到用于所有催化反应的单一反应温度和压力(例如约350℃至600℃、约400℃至500℃、约350℃至450℃、或约400℃和1-2atm),过程的高效率是出乎意料的。当加工常规原料时,该温度/压力区域一般并非充分适合于氢化。然而,在加工期间产生反应性单体中间产物的催化官能团和含氧原料(包括芳香族CHO聚合物原料)的独特组合优化反应的总体热力学和动力学。因此,三种反应(解聚、水-煤气变换和氢化)能够在固定床和流化床反应器的较低温度和大气压条件下有效催化,即使这些反应体积对于组合物中的所有催化剂并非最佳的。
实例
对照微球体(“对照”)的制备:仅由煅烧高岭土粘土基体组分组成(即不含催化剂)的阴性(非催化)对照微球体,由如美国专利号4,493,902中所述的喷雾干燥的高岭土浆料进行制备,所述美国专利以引用的方式并入本文。
基础催化剂微球体(“基础”)的制备:如以引用的方式并入本文的美国专利号7,375,048中所述,通过混合按重量计15%的非催化对照微球体(上文),按重量计35%的STAMINATM FCC催化剂(在高岭土粘土微球体基体中原位结晶的Y型沸石,BASF),以及通过使含有沸石、高岭土和低表面积氧化铝的浆料喷雾干燥产生的按重量计50%的ZSM-5混合,来制备仅包含Y型沸石和ZSM-5沸石催化剂的基础催化剂组合物。STAMINATM FCC催化剂包括按重量计约40%的沸石,并且ZSM-5组合物包括至少约30重量%的ZSM-5。相应地,催化剂组合物的Y型沸石组分代表按重量计约14%,并且催化剂组合物的ZSM-5组分代表按重量计至少约15%,其中总沸石组分为按基础催化剂的重量计约29%。在共混和测试之前,两种FCC组分均通过在蒸汽的存在下加热至815℃共4小时进行水热老化。
实验催化剂I(“EC I”)的制备:将基础催化剂组合物的非催化对照微球体组分替换为按重量计7.5%的水-煤气变换催化剂(在Mo促进的Al2O3上的Pt和Re氧化物,5.6重量%PtO2/3重量%ReO2O7)和7.5重量%的氢化催化剂。水-煤气变换催化剂如下制备:催化剂载体用钼酸二钠(钼酸钠盐脱水物)水溶液进行浸渍,随后为在300℃下煅烧3小时。浸渍的载体随后用氯铂酸水溶液浸渍,并且再次在300℃下煅烧3小时。最后,样品用过铼酸铵水溶液浸渍,并且随后在120℃下干燥过夜,随后为以5℃/分钟煅烧至500℃共2小时。氢化催化剂是含有按重量计60百分比的氧化铝上镍的商业氢化催化剂(Ni 3298)。水-煤气变换催化剂和氢化催化剂无需任何进一步失活而使用。水-煤气变换催化剂和氢化催化剂作为粉末混合到组合物内。
实验催化剂II(“EC II”)的制备:将基础催化剂组合物的非催化对照微球体组分替换为按重量计7.5%的高温水-煤气变换催化剂(在Mo促进的Al2O3上的Pt和Re氧化物,5.6重量%PtO2/3重量%ReO2O7)。水-煤气变换无需任何进一步失活而使用。水-煤气变换催化剂作为粉末混合到组合物内。
木质素的解聚和单芳香族化合物的生产:将木质素原料以5:1至9:1的催化剂/原料比分别与基础催化剂组合物以及实验催化剂I和实验催化剂II混合,并且置于固定流化床反应器中且加热至400℃的反应温度。将阴性对照微球体与木质素原料混合用于阴性对照反应,其中催化剂/原料比为0:1。在达到反应温度后,允许反应进行15分钟。在反应结束后收集且分析产物。***用氮连续吹扫。不凝性气体通过内联GC-MS进行分析。液体产物在水浴中冷凝,并且收集用于通过HT-Sim Dis和DHA分析和分类,其方式类似于得自汽油裂化的烃产物的分析。这些程序提供了基于沸点产物进入范畴内的定量分析和一些产物组分的定性鉴定。保留催化剂样品用于焦炭/炭分析。
结果
水-煤气变换反应:与非催化对照和基础催化剂两者相比较,对于实验催化剂I观察到产物气体中的CO减少。与阴性对照和基础催化剂相比较,CO的减少伴随产物气体中的氢和二氧化碳增加。这些结果指出WGS反应在固定床反应器的反应条件下有效进行。
表1
以重量%表示的气体得率
表2
以重量%表示的液体得率
与阴性对照相比较,基础催化剂(仅沸石)产生总液体得率的增加。尽管关于实验催化剂I的总液体得率略微小于基础催化剂,但所需单体(<220℃)的产生更高,并且二聚体/三聚体(220℃-340℃)和寡聚物(>340℃)的产生更低。
与阴性对照(52.95重量%)相比较,对于基础催化剂(43.11重量%)和实验催化剂(37.43重量%)两者均观察到焦炭的减少,但对于实验催化剂,焦炭的减少更大。这些结果提示使用实验催化剂通过解聚产生的单芳香族化合物通过由水-煤气变换反应的原位氢生成和通过氢化催化剂的氢化同时得到稳定。
表3
以重量%表示的焦炭和单体得率
样品进一步进行测试且测量,以获得来自有机液体的气体得率。再次,实验催化剂I获得更低量的焦炭,以及几乎两倍的有价值的芳香族产物(39.4相对于19.85)。
表4
表4显示了由每种反应样品产生的液体的碳、氢和氧含量。根据该数据,明确的是实验催化剂I和II提供氧去除中的显著优点,其中实验催化剂II显示与非催化反应相比较超过50%的氧去除。
表5
*油的重量
表6
经由2D TOF-MS定量的来自在400℃下热解的有机液体级分的选择组分,其中值作为有机液体的重量百分比给出。
基于根据组分分类的液体产物,明确的是本发明的催化剂混合物提供了优点,并且在催化剂混合物中的不同官能团的确在定制选择性中起作用。虽然PAH对于每种催化剂更高,但更重的组分减少,指示催化剂混合物能够阻止这些焦炭前体。对于每种催化剂混合物,芳香族化合物的百分比增加。具体地,实验催化剂II产生是对照几乎5倍的芳香族化合物,明显以苯酚化合物为代价。产物中的这种变换选择性指示催化剂混合物在CFP期间稳定单芳香族化合物。与构成大量液体产物的苯酚衍生物相比较,纯芳香族化合物的得率仍很小。表6列出了液体产物的十种最常见组分,以及对于三种催化剂该组分的重量百分比。2-甲氧基-苯酚(愈创木酚)和1,2苯二酚(儿茶酚)为两种最常见的苯酚衍生物。这两种芳香族化合物是许多工业价值链条中的关键化学中间产物。在实验催化剂II的情况下,超过50%的总液体级分由代表来自单一过程步骤的相对纯的产物流的这两种组分组成。
尽管本发明在本文中已就特定实施例而言进行描述,但应理解这些实施例仅是本发明的原理和应用的例证。对于本领域技术人员显而易见的是,可对本发明的方法和仪器作出各种修饰和变化,而不背离本发明的精神和范围。因此,预期本发明包括在所附权利要求及其等价物范围内的修饰和变化。
Claims (26)
1.一种用于原料的单阶段催化性快速热解的催化剂混合物,所述催化剂混合物包括:
a)至少一种裂化催化剂;
b)多相过渡金属水-煤气变换催化剂;和任选的
c)至少一种氢化催化剂。
2.根据权利要求1所述的催化剂混合物,其中所述裂化催化剂是选自下述的沸石裂化催化剂:FAU、CHA、MOR骨架类型、ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、TH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON、MFI、LTA、BEA骨架类型、ZSM-5、镁碱沸石、沸石Y、沸石β、丝光沸石、MCM-22、ZSM-23、ZSM-57、SUZ-4、EU-1、ZSM-11、(S)AIPO-31、SSZ-23、SAPO、ALPA和MeALPO。
3.根据权利要求2所述的催化剂混合物,其中所述至少一种沸石裂化催化剂选自沸石Y、ZSM-5及其混合物。
4.根据权利要求2所述的催化剂混合物,其中所述至少一种沸石裂化催化剂是以5:1至1:5比率的至少一种大孔沸石和至少一种小孔沸石的混合物。
5.根据权利要求1所述的催化剂混合物,其中所述多相过渡金属水-煤气变换催化剂包括至少一种金属氧化物、以及任选促进的载体。
6.根据权利要求5所述的催化剂混合物,其中所述金属氧化物选自铂、铼、钴及其混合物,并且所述载体选自Al2O3和二氧化硅,并且所述任选促进剂选自铈、钼和钨。
7.根据权利要求6所述的催化剂混合物,其中所述水-煤气变换催化剂包括在Mo促进的Al2O3载体上的铂(Pt)氧化物和铼(Re)氧化物。
8.根据权利要求1所述的催化剂混合物,其中所述至少一种氢化催化剂包括选自镍(Ni)、铜(Cu)、锌(Zn)及其组合的金属。
9.根据权利要求8所述的催化剂混合物,其中所述氢化催化剂包括Ni。
10.根据权利要求1所述的催化剂混合物,其中所述裂化催化剂或所述氢化催化剂中的至少一种负载于固体载体上。
11.根据权利要求10所述的催化剂混合物,其中所述裂化催化剂或所述氢化催化剂中的至少一种负载于多孔微球体上。
12.根据权利要求11所述的催化剂混合物,其中所述多孔微球体为直径约70-90μm。
13.根据权利要求11所述的催化剂混合物,其中所述多孔微球体具有直径约90-110nm的孔。
14.根据权利要求11所述的催化剂混合物,其中所述裂化催化剂在所述多孔微球体的孔内原位形成,并且所述水-煤气变换催化剂和氢化催化剂作为粉末或颗粒掺入所述微球体中或掺入所述微球体上。
15.根据权利要求1所述的催化剂混合物,其中所述催化剂混合物包括约40-85重量%的所述裂化催化剂、约5-40重量%的所述多相过渡金属水-煤气变换催化剂、以及任选的约3-20重量%的所述氢化催化剂。
16.根据权利要求15所述的催化剂混合物,其中所述催化剂混合物包括约50-80重量%的所述裂化催化剂、约7-20重量%的所述多相过渡金属水-煤气变换催化剂、以及任选的约7-10重量%的所述氢化催化剂。
17.一种用于由包含含氧聚合物的原料产生单芳香族化合物产物的方法,所述方法包括:
a)评价所述原料的氧含量;
b)在一步或单阶段中,使所述原料与包括至少一种裂化催化剂、多相过渡金属水-煤气变换催化剂和任选的至少一种氢化催化剂的催化剂混合物反应;和
c)回收所述单芳香族化合物产物。
18.根据权利要求17所述的方法,其中所述反应在约350℃至600℃下发生。
19.根据权利要求17所述的方法,其中所述原料具有约15-50%的氧含量。
20.根据权利要求19所述的方法,其中所述反应基本上无溶剂或其他外部添加剂而发生。
21.根据权利要求17所述的方法,其中所述原料具有小于约15重量%的氧含量。
22.根据权利要求21所述的方法,其中所述方法还包括将水或蒸汽加入所述反应混合物内。
23.根据权利要求17所述的方法,其中所述原料选自原始生物质、经加工的生物质的团块、农业残渣、木片和木材残渣、和能源作物、粪便、市政废物和得自纤维素的酶促加工的生物质。
24.根据权利要求23所述的方法,其中所述原料是含木质素生物质。
25.根据权利要求17所述的方法,其中所述回收的单芳香族化合物包括下述中的至少一种:苄基化合物、苯酚化合物、2-甲氧基-苯酚、1,2-苯二酚、4-乙基-2-甲氧基-苯酚、2-甲氧基-6-甲基苯酚、2-甲氧基-4-(1-丙烯基)-苯酚、苯酚、2-甲氧基-4-丙基-苯酚、乙酮、1-(4-羟基-3-甲氧基苯基)-苯酚、3-甲基-苯酚、2-甲氧基-4-甲基苯酚。
26.根据权利要求17所述的方法,其中所述方法在循环流化床催化裂化(FCC)***中实现。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111215129A (zh) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | ReOx/HZSM-5催化裂解木质素碳碳键的方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10155908B2 (en) * | 2012-03-07 | 2018-12-18 | Research Triangle Institute | Catalyst compositions and use thereof in catalytic biomass pyrolysis |
RU2603134C1 (ru) * | 2015-11-17 | 2016-11-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Нижегородский государственный университет им. Н.И. Лобачевского" | Катализатор для пиролиза углеводородной смеси с1-с4 и способ его получения |
WO2018195422A1 (en) | 2017-04-20 | 2018-10-25 | Spero Energy, Inc. | Extraction of natural ferulate and coumarate from biomass |
WO2019108959A1 (en) * | 2017-12-01 | 2019-06-06 | Spero Renewables, Llc | Lignin conversion to phenolic molecules using transition metal catalysts |
FR3081340B1 (fr) * | 2018-05-24 | 2020-06-26 | IFP Energies Nouvelles | Catalyseur comprenant un melange d'une zeolithe de type structural afx et d'une zeolithe de type structural bea et au moins un metal de transition pour la reduction selective de nox |
CN112439446B (zh) * | 2019-09-04 | 2022-03-01 | 中国科学院大连化学物理研究所 | 双金属催化剂的制备及应用于催化解聚木质素c-c键方法 |
KR102392252B1 (ko) | 2020-03-05 | 2022-04-28 | 김성연 | 영상처리 기술을 적용한 버섯 객체 생장 모니터링 방법 |
US11274068B2 (en) | 2020-07-23 | 2022-03-15 | Saudi Arabian Oil Company | Process for interconversion of olefins with modified beta zeolite |
US11332678B2 (en) | 2020-07-23 | 2022-05-17 | Saudi Arabian Oil Company | Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst |
US11420192B2 (en) | 2020-07-28 | 2022-08-23 | Saudi Arabian Oil Company | Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts |
US11154845B1 (en) | 2020-07-28 | 2021-10-26 | Saudi Arabian Oil Company | Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts |
US11142703B1 (en) | 2020-08-05 | 2021-10-12 | Saudi Arabian Oil Company | Fluid catalytic cracking with catalyst system containing modified beta zeolite additive |
KR102490099B1 (ko) * | 2020-11-25 | 2023-01-18 | 한국에너지기술연구원 | 가스화 및 연소 공정 부산물을 이용한 타르 개질 공정 및 촉매 |
EP4056267A1 (de) * | 2021-03-11 | 2022-09-14 | Heraeus Deutschland GmbH & Co. KG | Verfahren und katalysator zur herstellung von phenolbausteinen aus lignin |
WO2023034859A1 (en) * | 2021-08-31 | 2023-03-09 | Georgia Tech Research Corporation | Continuous reaction systems and methods |
US11618858B1 (en) | 2021-12-06 | 2023-04-04 | Saudi Arabian Oil Company | Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts |
CN114184722A (zh) * | 2021-12-17 | 2022-03-15 | 南亚新材料科技(江西)有限公司 | 一种利用超高效聚合物凝胶色谱法分析酸催化木质素解聚产物的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030115792A1 (en) * | 2001-10-05 | 2003-06-26 | Shabtai Joseph S | Process for converting lignins into a high octane blending component |
CN102015969A (zh) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物 |
US20110201854A1 (en) * | 2010-02-17 | 2011-08-18 | Kocal Joseph A | Low oxygen biomass-derived pyrolysis oils and methods for producing the same |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4493902A (en) | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
US4802971A (en) | 1986-09-03 | 1989-02-07 | Mobil Oil Corporation | Single riser fluidized catalytic cracking process utilizing hydrogen and carbon-hydrogen contributing fragments |
DE60044334D1 (de) * | 1999-03-18 | 2010-06-17 | Panasonic Elec Works Co Ltd | Verwendung eines katalysators für die wasser-gas-umwandlungsreaktion, verfahren zur entfernung von krgieerzeugung aus einer brennstoffzelle |
US20030089640A1 (en) | 2001-10-17 | 2003-05-15 | Rostam Madon | FCC catalysts for feeds containing nickel and vanadium |
US6656347B2 (en) | 2000-09-22 | 2003-12-02 | Engelhard Corporation | Structurally enhanced cracking catalysts |
EP1393804A1 (de) | 2002-08-26 | 2004-03-03 | Umicore AG & Co. KG | Mehrschichtiger Katalysator zur autothermen Dampfreformierung von Kohlenwasserstoffen und Verfahren zu seiner Verwendung |
US7375048B2 (en) | 2004-04-29 | 2008-05-20 | Basf Catalysts Llc | ZSM-5 additive |
CN100391610C (zh) * | 2005-08-15 | 2008-06-04 | 中国石油化工股份有限公司 | 含分子筛的催化裂解流化床催化剂 |
US7357911B2 (en) * | 2005-12-16 | 2008-04-15 | Basf Catalysts Llc | Process conditions for Pt-Re bimetallic water gas shift catalysts |
EP1852493A1 (en) * | 2006-05-05 | 2007-11-07 | BIOeCON International Holding N.V. | Hydrothermal treatment of carbon-based energy carrier material |
EP2054488A2 (en) * | 2006-07-17 | 2009-05-06 | BIOeCON International Holding N.V. | Catalytic pyrolysis of fine particulate biomass, and method for reducing the particle size of solid biomass particles |
CN101172924B (zh) * | 2006-11-02 | 2010-09-01 | 中国石油化工股份有限公司 | 高选择性芳烃烷基转移和脱烷基增产二甲苯反应方法 |
US20090095657A1 (en) * | 2006-11-07 | 2009-04-16 | Saudi Arabian Oil Company | Automation and Control of Energy Efficient Fluid Catalytic Cracking Processes for Maximizing Value Added Products |
BRPI0817040A2 (pt) | 2007-08-01 | 2015-03-24 | Nagarjuna Energy Private Ltd | Processo para produção de compostos orgânicos de baixo peso molecular de materiais carbonáceos. |
US8350108B2 (en) * | 2008-08-27 | 2013-01-08 | Virent, Inc. | Synthesis of liquid fuels from biomass |
US8404908B2 (en) | 2009-10-13 | 2013-03-26 | Uop Llc | Process for lignin conversion to chemicals or fuels with H2 generated from lignin depolymerization products |
US8772558B2 (en) | 2011-07-26 | 2014-07-08 | Uop Llc | Methods and apparatuses for producing aromatic hydrocarbon-containing effluent |
EP2751223A1 (en) | 2011-09-01 | 2014-07-09 | The University of Massachusetts | Method for producing fluid hydrocarbons |
SG11201405635WA (en) * | 2012-04-02 | 2014-11-27 | Saudi Arabian Oil Co | Multimetal zeolites based catalyst for transalkylation of heavy reformate to produce xylenes and petrochemical feedstocks |
-
2015
- 2015-02-06 BR BR112016018282-0A patent/BR112016018282B1/pt active IP Right Grant
- 2015-02-06 CA CA2939090A patent/CA2939090C/en active Active
- 2015-02-06 CN CN201580018022.3A patent/CN106163655B/zh active Active
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- 2015-02-06 EP EP15747048.5A patent/EP3102324B1/en active Active
-
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- 2017-05-25 US US15/604,942 patent/US10137442B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030115792A1 (en) * | 2001-10-05 | 2003-06-26 | Shabtai Joseph S | Process for converting lignins into a high octane blending component |
CN102015969A (zh) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物 |
US20110201854A1 (en) * | 2010-02-17 | 2011-08-18 | Kocal Joseph A | Low oxygen biomass-derived pyrolysis oils and methods for producing the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111215129A (zh) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | ReOx/HZSM-5催化裂解木质素碳碳键的方法 |
CN111215129B (zh) * | 2018-11-25 | 2023-02-24 | 中国科学院大连化学物理研究所 | ReOx/HZSM-5催化裂解木质素碳碳键的方法 |
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