CN109195702A - 用于烃裂化的发热催化剂 - Google Patents
用于烃裂化的发热催化剂 Download PDFInfo
- Publication number
- CN109195702A CN109195702A CN201780028936.7A CN201780028936A CN109195702A CN 109195702 A CN109195702 A CN 109195702A CN 201780028936 A CN201780028936 A CN 201780028936A CN 109195702 A CN109195702 A CN 109195702A
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- China
- Prior art keywords
- catalyst
- metal oxide
- fever
- mfi zeolite
- hydrocarbon
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 298
- 238000005336 cracking Methods 0.000 title claims abstract description 104
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 104
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 104
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 103
- 206010037660 Pyrexia Diseases 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 93
- 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 61
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 59
- 239000010457 zeolite Substances 0.000 claims abstract description 59
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 57
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 56
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- 150000004690 nonahydrates Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 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 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
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- 239000004332 silver Substances 0.000 claims description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
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- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- XYUOGBDVXDNPHH-UHFFFAOYSA-N copper trihydrate Chemical compound O.O.O.[Cu] XYUOGBDVXDNPHH-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
一种制备用于烃裂化的发热催化剂的方法。该方法包括提供至少一种具有Si/Al摩尔比为15或更大的丝光沸石骨架反转(MFI)沸石,并提供至少一种金属氧化物前体。此外,至少一种金属氧化物前体分散在MFI沸石催化剂的微结构内。该方法另外包括煅烧具有分散在MFI沸石催化剂的微结构内的至少一种金属氧化物前体的发热材料,以原位形成至少一种金属氧化物。发热催化剂包括比例为50:50至95:5的至少一种MFI沸石和至少一种金属氧化物。另外,提供了在烃裂化过程中使用发热催化剂的相关方法。
Description
相关申请的交叉引用
本申请要求2016年5月12日提交的美国临时申请序列号62/335,213的权益,所述申请以引用的方式并入本文中。
背景
技术领域
本公开的实施方案一般地涉及用于烃裂化的发热催化剂,并且具体地涉及制备发热催化剂的方法和在烃裂化过程中使用该发热催化剂的方法。
背景技术
目前用于生产轻质烯烃如乙烯和丙烯的商业技术包括热裂化或蒸汽裂化以及催化裂化。蒸汽裂解是一种非催化过程,其在约850℃的升高的反应温度下操作,并且需要蒸汽稀释以控制选择性并保持可接受的回路寿命。它是迄今为止化学工业中耗能最多的工艺。发现单独的石脑油蒸汽裂化器的热解部分消耗了总工艺能量的约65%并且占总能量损失的约75%。此外,该工艺对进料变化极为敏感,并引起一些环境问题。它不适合满足预期的丙烯增长需求,因为它生产乙烯作为主要产品,并且它几乎不能控制丙烯与乙烯(P/E)比率。相反,催化裂化,特别是用固体酸催化剂的流化催化裂化(FCC)产生具有相对较高P/E比的产物,并且在500-650℃的较低温度下操作。在FCC方法中,催化剂悬浮在流化床中上升的进料烃流中。预热的烃进料通过进料喷嘴喷入截锥体/提升管的底部,在那里它与热的流化催化剂在500-650℃接触。热催化剂蒸发进料并催化裂化反应以将高分子量分子分解成更轻的组分,包括液化石油气(LPG)、汽油和柴油。然后,“用过的”催化剂流入流化床再生器,其中使用空气或在某些情况下空气加氧气来燃烧焦炭以恢复催化剂活性并且还为下一个反应循环提供必要的热量。然后“再生”催化剂流到提升管的底部,重复循环。
烃裂化工业已经投入了大量努力来最大化吸热烃转化过程的能量效率,尤其是裂化,而不损害产率和转化率。例如,FCC理想地是热中性的,其中再生器中的焦炭燃烧加速吸热裂化反应。然而,实际上,由焦炭燃烧产生的这种热量通常是不足的,特别是对于具有高氢/碳(H/C)比的较轻的进料。先前已采用若干技术来克服能量缺乏,例如注入过量空气以促进完全燃烧。然而,注入过量空气会显着增加副反应以及运营和资本成本。或者,已经尝试将计算量的芳族重质燃料(称为火炬油)注入再生器部分以提供额外的热能。该方法虽然有效,但通常导致形成非氧化裂化产物。非氧化裂化产物可能在催化剂床中形成热点,在蒸汽存在下,热点可能导致催化剂床失活和局部永久性损坏。
发明内容
鉴于所提供的背景,持续需要开发有效且经济的途径来裂解原油以产生高需求的石化结构单元,包括乙烯、丙烯、丁烯、苯、甲苯和二甲苯以及其他烃类如汽油、常压瓦斯油(ago)和减压瓦斯油(vgo)。
本公开的实施方案涉及制备和在烃裂化工艺中使用发热催化剂以补充吸热烃裂化的能量需求的方法。由于传统上烃裂化所需的能量成本高,因此本公开的方法和***具有工业实用性,具体地在石油和天然气工业中。不局限于理论,添加本公开的发热催化剂以帮助烃裂解过程变为能量中性或接近能量中性,从而降低与烃裂解相关的总能量成本。
根据一个实施方案,提供了制备用于烃裂化的发热催化剂的方法。该方法包括提供至少一种丝光沸石骨架反转(MFI)沸石催化剂,其具有15或更高的Si/Al摩尔比并提供至少一种金属氧化物前体。此外,该方法包括将至少一种金属氧化物前体分散在MFI沸石催化剂的微结构内。随后,该方法包括煅烧金属氧化物前体浸渍的MFI沸石催化剂以形成发热催化剂。MFI沸石催化剂与金属氧化物的比例以重量计为50:50至95:5。催化剂可以用粘合剂、粘土、分散剂和其他添加剂进一步改性。
根据另一个实施方案,提供了一种在烃裂化过程中使用发热催化剂的方法。该方法包括提供催化剂床反应器,其包括设置在催化剂床反应器中的发热催化剂的催化剂床。发热材料由至少一种具有Si/Al摩尔比为15或更大的丝光沸石骨架反转(MFI)沸石催化剂和分散在MFI沸石催化剂微结构内的至少一种金属氧化物形成。该方法还包括将烃进料引入催化剂床反应器并裂化烃进料以产生裂化产物。根据至少一个实施方案,裂化产物包括轻质C1-C4烃。
所描述的实施方案的另外的特征和优点将在下文的具体实施方式中阐述,并且本领域的技术人员将部分地从所述描述容易地清楚,或通过实践所描述的实施方案(包括下文的具体实施方式、权利要求以及附图)而认识到。
应理解,前述一般描述和以下具体实施方式描述了各种实施方案,并且旨在提供概述或框架以用于理解所主张的主题的性质和特征。包括附图以提供对各种实施方案的进一步理解,并且所述附图被并入本说明书中并且构成本说明书的一部分。附图说明了描述的各种实施方案,并且与说明书一起用于解释所要求保护的主题的原理和操作。
附图说明
图1是根据本公开的一个或多个实施方案的用于操作的实验室规模反应器***的示意图。
图2是根据本公开的一个或多个实施方案的CuO/H-ZSM-5催化剂的背散射电子扫描电子显微镜图像。
图3是氧化铝上负载的20%CuO的程序升温还原试验。
图4是CuO/H-ZSM-5和未改性H-ZSM-5的催化剂床温度曲线,重时空速为3.5hr-1,初始温度为550℃。
图5是CuO/H-ZSM-5和未改性H-ZSM-5的催化剂床温度曲线,重时空速为8.4hr-1,初始温度为550℃。
图6是CuO/H-ZSM-5在重时空速为8.4hr-1、初始温度为550℃以及CuO/H-ZSM-5在重时空速为8.4hr-1和初始温度588℃的催化剂床温度曲线。
具体实施方式
现在将详细参考制备用于烃裂化的发热催化剂和使用本发明的发热催化剂的改进的烃进料裂化的方法的实施方案。如前所述,烃裂化是一种吸热过程。通过将裂化催化剂与发热金属氧化物组合,传统的吸热烃裂化过程可以变为热中性或接近热中性。具体地,当包括在本公开的烃裂化过程中时,分散在整个裂化催化剂中的金属氧化物通过反应器中的还原反应产生放热。所述放热可以提供用于吸热烃裂化过程所需的另外的热量。另外,当还原的催化剂暴露于氧化条件时,再生器中的氧化反应产生额外的热量。再生器中由氧化反应产生的热量增加了发热催化剂的温度,当发热催化剂再循环回到反应器中时,这又增加了烃进料的转化率。
提供了一种制备用于烃裂化的发热催化剂的方法。将裂化催化剂和至少一种金属氧化物前体结合在一起。具体地,至少一种金属氧化物前体分散在裂化催化剂的微结构内。在将至少一种金属氧化物前体分散在裂化催化剂的微结构内的情况下,将发热催化剂煅烧以将至少一种金属氧化物前体转化为至少一种金属氧化物。
在至少一个实施方案中,发热催化剂中MFI沸石催化剂与金属氧化物的比例基于重量为50:50至95:5。在催化剂和金属氧化物百分比之间存在折衷。具体地,金属氧化物的重量百分比的增加在还原反应期间提供额外的发热金属氧化物,从而允许更热或更长的持续发热。然而,金属氧化物百分比的增加可能导致MFI沸石催化剂的催化剂活性降低。在各种进一步的实施方案中,发热催化剂中MFI沸石催化剂与金属氧化物的比例基于重量为70:30至85:15,基于重量为70:30至80:20,并且基于重量为为75:25和85:15。在至少一个实施方案中,发热催化剂中MFI沸石催化剂与金属氧化物的比例基于重量为79:21至81:19。不希望受理论束缚,据信,除了产生热量之外,金属氧化物还可以以可能影响裂化活性的方式改性MFI沸石上的酸性位点。酸性位点的改性可最终增加或降低MFI沸石催化剂的催化剂活性,并调节所得物质对产物流的选择性。酸性位点的改性取决于金属氧化物、MFI沸石和在发热催化剂中使用的每种的量。
考虑各种组分用于裂化催化剂。在一个或多个实施方案中,裂化催化剂床可包括硅铝酸盐沸石、硅酸盐(例如硅质岩)或钛硅酸盐。在进一步的实施方案中,固体裂化催化剂是具有丝光沸石骨架反转(Mordenite Framework Inverted)(MFI)结构的硅铝酸盐沸石。例如但不作为限制,MFI沸石催化剂可以是ZSM-5催化剂。在另一个实施方案中,ZSM-5催化剂可以是H-ZSM-5催化剂,其中至少一部分ZSM-5催化剂离子交换位置被H+离子占据。此外,MFI沸石催化剂,例如H-ZSM-5催化剂,可具有至少15的Si/Al摩尔比。在进一步的实施方案中,MFI沸石催化剂可具有至少20,或至少35,或至少45的Si/Al摩尔比。另外,MFI沸石催化剂的平均粒度可根据应用而变化。例如,当用于流体催化应用时,MFI沸石催化剂的平均粒度可以为50至120微米(μm),或者当用于固定床应用时,其平均粒径为1/16”至1/4”。
此外,金属氧化物前体分散在裂化催化剂的微结构内并原位煅烧以将金属氧化物前体转化为金属氧化物。在裂化催化剂的微观结构内分散至少一种金属氧化物前体使金属氧化物紧邻裂化催化剂的吸热裂化位点,从而使发热催化剂的发热方面更有效。在裂化催化剂的微观结构内分散至少一种金属氧化物前体与仅仅裂化催化剂和金属氧化物的物理混合形成对比。物理混合仅将金属氧化物提供给裂化催化剂颗粒表面附近的裂化催化剂的吸热裂化位点,而不是靠近裂化催化剂微结构内的附加吸热裂化位点。金属氧化物前体在裂化催化剂的微观结构中的分散有助于避免可能仅仅是由于物理混合裂化催化剂和金属氧化物而产生的在催化剂床中的温度梯度和催化剂床内的热点。应当理解,可以将发热催化剂提供给烃裂化***,其中金属氧化物前体为还原形式,随后其在烃裂化***操作期间通过经再生器的第一通道氧化成金属氧化物。
在各种实施方案中,通过湿浸渍、干浸渍、初湿浸渍、沉淀、离子交换、电解沉积、沉积-沉淀、化学气相沉积和火焰喷雾热解中的至少一种将至少一种金属氧化物前体分散在裂化催化剂的微结构内。每种方法都允许金属氧化物前体分散在裂化催化剂的整个微结构中,这仅仅用物理混合是不可能的。在各种实施方案中,金属氧化物分散在裂化催化剂的整个微结构中。在一个或多个实施方案中,金属氧化物前体在裂化催化剂的微结构内的分散包括将金属氧化物前体溶解在有机溶剂(例如甲醇、乙醇、丙酮或水)中的步骤,并逐滴加入至裂化催化剂同时搅拌所得的发热催化剂。在进一步的实施方案中,该方法另外包括干燥具有分散在裂化催化剂微结构内的金属氧化物前体的裂化催化剂。干燥步骤包括在90℃至120℃下干燥至少1小时。进一步的实施方案包括在90℃至120℃下干燥至少3小时,在95℃至115℃下干燥至少3小时,以及在98℃至112℃下干燥至少3小时。
如前所述,将具有分散在裂化催化剂微结构内的金属氧化物前体的裂化催化剂煅烧以原位产生金属氧化物。在一个或多个实施方案中,在400℃至800℃的空气中实现发热催化剂的煅烧,其包含具有分散在裂化催化剂的微观结构中的金属氧化物前体的裂化催化剂。将煅烧过程延长足够的时间以使金属氧化物前体原位转化为金属氧化物,通常持续3小时或更长时间。进一步的实施方案包括在700℃至800℃下煅烧至少3小时,在550℃至650℃下煅烧至少4小时,并在600℃至700℃下干燥至少3小时。
金属氧化物前体向金属氧化物的转化提供了分散在裂化催化剂的微观结构中的位点,用于由于金属氧化物的还原反应而产生热量。在至少一个特定实施方案中,产生的金属氧化物是氧化铜。在各种实施方案中,金属氧化物是铁、铜、锌、铬、钼、钒、铈、锰、铋、银、钴、钒、锆、钨、镁的氧化物中的至少一种及其组合。
在至少一个实施方案中,金属氧化物前体是硝酸金属盐的水合物。非限制性实例包括硝酸铜三水合物(Cu(NO3)2·3H2O)、硝酸钴(II)六水合物(Co(NO3)2·6H2O)和硝酸铬(III)九水合物(Cr(NO3)3·9H2O)。
分散在裂化催化剂的微结构内的至少一种金属氧化物化学键合到微结构上。浸渍或其它分散技术将金属氧化物前体推入裂化催化剂的微结构内,相反,仅物理混合使裂化催化剂和金属氧化物颗粒完全分离。此外,浸渍可以将氧化物金属化学地结合到催化剂表面和孔内部的官能团中。裂化催化剂的微观结构内的分散也使金属氧化物靠近催化剂中的活性位点,相反地,物理混合使金属氧化物和催化剂中的活性位点保持分离。
在一个或多个实施方案中,发热催化剂还包含促进剂。促进剂的非限制性实例包括碱金属、碱土金属、稀土金属、过渡金属、磷和它们的组合。
所产生的用于烃裂化的发热催化剂可用于烃氧化裂化过程中的烃裂化***。图1的烃裂化***是为如下本讨论提供的实验室设置;然而,应理解,本***和方法涵盖其他配置,包括大规模和工业过程方案。
参考图1的实施方案,显示了用于裂解烃进料4的实验室规模的烃裂化***100,其具有至少一个催化剂床反应器10。具体地,烃裂化***100利用在催化剂床反应器中形成催化剂床的先前讨论的发热催化剂进行烃进料4的催化烃裂化。
烃进料4可以指衍生自石油、煤液或生物材料的任何烃源。烃源的实例包括全范围原油、蒸馏原油、残油、顶部原油、液化石油气(LPG)、石脑油、瓦斯油、来自炼油厂的产物流、来自蒸汽裂解过程的产物流、液化煤、从油或沥青砂中回收的液体产物、沥青、油页岩、生物质烃等。在将在随后段落中描述的具体实例中,烃进料4可包括正己烷、石脑油、混合丁烯、和乙烯。当对这些组分的需求提高时,可包括C4-C5、C9和C9+烃以重新裂化并产生增值组分。正己烷仅是长链烃的一个实例,其目前定义为具有至少6个碳的烃碳链。
再次参考图1,烃裂化***100可包含具有至少一个催化剂床反应器10的反应器***,以及任选的另外的反应器和单元。例如,这些另外的任选单元可包括连接到至少一个催化剂床反应器10的预热器12和另外的加热器或热交换器18。
如图所示,该催化剂床反应器10可包括床设置在催化剂床反应器10中的发热催化剂的催化剂床14。如前所述,催化剂床反应器10的操作导致烃进料4的裂解以产生裂化产物40,其中裂化产物40包含轻C1-C4烃,例如乙烯和丙烯,以及重C5+烃。裂化产物40还可包含BTX芳族化合物(苯、甲苯和二甲苯异构体)。裂化产物40中组分的比例根据进料类型、反应参数和催化剂参数而变化。利用发热催化剂作为催化剂床反应器10的催化剂床14减少或消除了在催化剂床中反应器10的额外热量的能量输入要求。具体地,当氧化物被还原时发热催化剂在催化剂床反应器10中经历放热反应,其抵消了吸热裂解过程,产生了热中性的整体烃裂化操作。另外,在一个或多个实施方案中,还原的金属氧化物可以在氧化气氛中再生以产生额外的热释放。
另外,由于它们的还原反应,金属氧化物的氢消除限制了氢转移反应,因此促进了烃向轻质烯烃的裂化。从产物流中除去氢气也消除了将所得轻质烯烃与氢气分离的昂贵且困难的过程。
在一个或多个实施方案中,催化剂床反应器10可以是固定床反应器、流化床反应器、浆料反应器或移动床反应器。在一个具体实施方案中,催化剂床反应器10是固定床反应器。在具有固定床反应器的一些实施方案中,组合的烃进料4和发热促进流2在催化剂床反应器10中的停留时间是在0.05秒至1小时的范围内。例如,对于柴油加氢处理液体进料的停留时间可接近1小时,并且在FCC应用中大体上在0.1至5秒的范围内。因此,在各种实施方案中,催化剂床反应器10中的停留时间为0.1秒至5秒或5分钟至1小时。在用于最佳烃裂化的组合的烃进料4的固定床反应器中所需的停留时间取决于的操作温度以及发热催化剂床和烃进料4组成。此外,在一个或多个实施方案中,床层空隙率,其表示由空隙所占据的体积分数是在0.2和1.0之间。在进一步的实施方案中,床层空隙率是在0.3和0.8之间。
另外,在具有固定床反应器的一个或多个实施方案中,发热催化剂的催化剂床14包括一层发热催化剂设置在一层未改性的裂化催化剂之前,发热催化剂包含具有金属氧化物分散在微结构内的裂化催化剂。在进一步的实施方案中,发热催化剂的催化剂床14包括一层发热催化剂设置在一层未改性的裂化催化剂之后,发热催化剂包含具有金属氧化物分散在微结构内的裂化催化剂。在另外的实施方案中,发热催化剂的催化剂床14可包括一层发热催化剂设置在至少两层未改性的裂化催化剂之间,发热催化剂包含具有金属氧化物分散在微结构内的裂化催化剂。
另外,在具有流化床反应器的一个或多个实施方案中,催化剂床14包含发热催化剂和裂化催化剂的混合物,该裂化催化剂没有分散在其微结构内的金属氧化物。
此外,催化剂床14可以预热。在一个或多个实施方案中,催化剂床14使用在通过催化剂床反应器10的管中的蒸汽或热气体进行加热。在进一步的实施方案中,催化剂床14在足够的流速下在含有加热的氮6和氧的气流中被预热,以加热催化剂床14。在各种实施方案中,预热的气流或蒸汽在450至650℃,或475至525℃,或490至510℃下加热。
参考图1,所述方法还可包括在催化剂床反应器10的上游预热烃进料4。可以在预热器12中实现烃进料4的此预热。如图所示,烃进料4可以在氮6和空气8的存在下加热。另外,可以在蒸汽、氢气、空气、氧气或它们的组合的存在下加热烃进料4。在一个实施方案中,预热器12可以将供应到催化剂床反应器10的烃进料的温度提高至至少200℃。进料预热器有助于减轻冷进料对催化剂床反应器10顶部的冷却,冷进料又会影响催化剂性能。
在一个或多个实施方案中,烃裂化***100还可包括设置在预热器12的上游的至少一个烃预热器18。一个或多个烃预热器或预热器18,如图1所示,提高供应到至少一个预热器12的烃进料的温度。在进一步的实施方案中,烃预热器18将供应给至少一个预热器12的烃进料的温度升高至至少100℃。烃预热器18可包括本领域普通技术人员熟悉的热交换器或类似的加热器装置。
烃裂化***100还可以包括如图所示的其他加热元件。例如,烃裂化***100可包括反应器炉20或围绕催化剂床反应器10、预热器12和烃预热器18的热箱22。反应器炉20可有助于在实验室规模或中试装置中保持催化剂床反应器10和预热器12的温度。类似地,热箱22用于保持催化剂床反应器10、预热器12和烃预热器18周围的热量,以减少热损失。
再次参考图1,裂化产物40可包含各种轻C1-C4烃和重C5+烃。在一个或多个实施方案中,裂化产物40具体包含丙烯、丁烯如2-反式丁烯、正丁烯、异丁烯和2-顺式丁烯、C5烯烃、芳烃、甲烷、乙烷、丙烷、丁烷和戊烷。裂化产物40的组分取决于烃进料4的组分以及裂化催化剂和金属氧化物二者的性质。
为了将裂化产物40中的轻烃与重烃分离,烃裂化***100还可包括至少一个液/气分离器24。液/气分离器24,其可以包括闪光槽等,基于所述裂化产物40的各个组分的沸点分离裂化产物40为多个产物流。具体地,在液/气分离器24中,可以从液/气分离器24的顶部蒸发出作为气相轻烃的轻烃流42,而液相重烃流44则从液/气分离器24的底部排出。
考虑进一步的反应以将所需的丙烯和乙烯从轻烃流42分离。例如,轻烃流42可以作为液态烃产物冷却和收集。此时,丙烯和乙烯可通过蒸馏或萃取方法分离。
在进一步的实施方案中,另外将蒸汽供应到烃裂化***100以控制反应的空速。在实施方案中,使去离子水通过蒸发器或过热器至直接进入催化剂床反应器10中的进料流。这种布置可以向催化剂床反应器10提供高达400℃的过热流。重时空速(WHSV)定义为每小时(hr)进料量的重量除以催化剂的重量。在各种实施方案中,反应的WHSV为1至100小时-1(hr-1)、3至9hr-1、3至4hr-1和8至9hr-1并且根据被催化的反应类型而变化。
发热催化剂的反应时间的限制因素是金属氧化物负载量。具体地,在裂化催化剂失活之前,金属氧化物还原产生的热量下降。因此,在至少一个实施方案中,氢气或其它可燃物质可以在单独的反应器中选择性地燃烧以产生额外的热量以加热吸热的烃裂化反应,超过还原金属氧化物向裂化催化剂活性位点提供额外热量的时间。
实施例
以下实施例是对本发明实施方案的说明,并且不旨在限制本公开所述实施方案的范围。
实施例1-CuO/H-ZSM-5催化剂:
制备Si/Al重量比为38的H-ZSM-5催化剂,其载有约20wt%的氧化铜(II)。提供购自Sigma-Aldrich的硝酸铜三水合物(Cu(NO3)2·3H2O)作为金属氧化物前体。将11.4克(g)硝酸铜三水合物完全溶解在3.7克去离子水中。随后,在搅拌下将溶解在去离子水中的硝酸铜三水合物逐滴添加到15g轻微压碎的ZSM-5中。将得到的固体在110℃的烘箱中干燥4小时,然后在空气中在650℃下煅烧4小时。图2显示了来自CuO/H-ZSM-5催化剂的背散射电子扫描电子显微镜(BSE-SEM)的输出图像。另外,电感耦合等离子体(ICP)分析证实沸石催化剂上最终的19.9%氧化铜载量。
参考图3,提供了负载在氧化铝上的20%CuO的程序升温还原(TPR)测试。制备负载在氧化铝上的CuO样品用于该测试,以单独确定铜的还原行为。TPR测试证实,CuO可以在350℃以上的反应温度下还原并产生热量。
实施例2-FeO/H-ZSM-5催化剂:
制备Si/Al重量比为38的H-ZSM-5催化剂,其负载有混合的铁(II和III)氧化物。将15g混合铁(II和III)氧化物加入到15g H-ZSM-5和20g作为粘合剂的α-氧化铝中。随后,加入30g水以产生稠度,其允许通过注射器容易地挤出。然后将混合物挤出并在100℃下干燥过夜。干燥后,将混合物在空气中在750℃下煅烧4小时(hr)。
实施例3-CoO/H-ZSM-5催化剂:
制备Si/Al重量比为38的H-ZSM-5催化剂,其载有约20wt%的氧化钴。提供六水合硝酸钴(II)(Co(NO3)2·6H2O)作为金属氧化物前体。将14.6克(g)硝酸钴(II)六水合物完全溶解在4.57克去离子水中。随后,在搅拌下将溶解在去离子水中的硝酸钴(II)六水合物滴加到15g轻微粉碎的ZSM-5中。将得到的固体在110℃的烘箱中干燥4小时,然后在空气中在650℃下煅烧4小时。
实施例4-CrO/H-ZSM-5催化剂:
制备Si/Al重量比为38的H-ZSM-5催化剂,其载有约20wt%的氧化铬。提供硝酸铬(III)九水合物(Cr(NO3)3·9H2O)作为金属氧化物前体。将22.1克(g)硝酸铬(III)九水合物完全溶解在13.9克去离子水中。随后,在搅拌下将溶解在去离子水中的硝酸铬(III)九水合物逐滴添加到15g轻微压碎的ZSM-5中。将得到的固体在110℃的烘箱中干燥4小时,然后在空气中在650℃下煅烧4小时。
烃进料4和轻烯烃(例如,乙烯和丙烯)的改进的转化率用实验测试进行了验证。获得实验数据以证明用金属氧化物改性沸石催化剂的效果。催化反应在固定床流动反应器***和流化提升管模拟器中进行。对于固定床实验,在不同条件下,将己烷提供给烃裂化***100实验装置。
将根据实施例1制备的催化剂装入反应器中。对于每个实施例,从南开大学催化剂公司(Nankai University Catalyst Company)获得Si/Al重量比为38的H-ZSM-5沸石催化剂。沸石催化剂含有30重量%的γ氧化铝作为粘合剂。用于对比未改性催化剂测试的未改性催化剂是H-ZSM-5,其Si/Al比为38,将其粉碎并筛分至5至850纳米(nm)或250至850nm、或425至850nm范围内的粒度。另外,用于氢进料的正己烷从Sigma-Aldrich获得并且是高效液相色谱(HPLC)级。
固定床流动反应器***具有两个串联连接的管式反应器。将用于测试的催化剂,例如实施例1的CuO/H-ZSM-5催化剂,安装在第二反应器中,同时使用第一反应器将己烷进料预热至反应温度。进料预热器可提高工艺的能效。另外,如果将冷进料直接引入催化剂床中,催化剂床的顶部将冷却并降低反应器的性能以及影响转化率和选择性。首先在气流下以0.154升/分钟(l/min)在550℃下活化新鲜催化剂1小时。在所需的反应温度下,将正己烷引入反应器中以开始反应。使用氮气作为稀释剂,在550℃和WHSV为3.5hr-1下进行反应。
参考图4,提供了随着反应时间的进行催化剂床温度曲线的比较。使用安装在催化剂床内的3点热电偶测量催化剂床温。使用氮气作为稀释剂,在550℃和WHSV为3.5hr-1下进行反应。未改性的H-ZSM-5催化剂的催化剂床温在550℃的反应温度下保持稳定。相反,根据实施例1制备的改性CuO/H-ZSM-5催化剂产生明显的放热反应。催化剂床温度从550℃的起始反应温度迅速升至597℃以上,表明随着反应的进行而降低之前反应的放热性。在初始加料后催化剂床温度的稳定降低被认为是氧化金属物质消失的结果,因为氧化的金属物质被还原,导致额外热量的产生减少。改性催化剂产生放热反应,在所选择的反应条件下催化剂床温度提高了近50℃。为了消除控制器的影响,将烘箱的温度设定在一定温度,使催化剂床在氮气流下保持在550℃。因此,当引入进料时,任何温度升高或降低都可归因于反应而不是控制器的影响。
随着烃进料的流速增加通过反应器,对放热裂化反应期间保持催化剂床温度的固定床反应器***的外部加热功能的要求增加。参考图5,提供了随着反应时间的进行催化剂床温度曲线的比较。使用氮气作为稀释剂,在550℃和WHSV为8.4hr-1下进行反应。反应参数与图4相同,但WHSV改为8.4hr-1。随着通过反应器的烃流速增加,根据实施例1制备的改性CuO/H-ZSM-5催化剂导致催化剂床温度床在550℃下保持基本稳定。相反,未改性的H-ZSM-5催化剂导致催化剂床温从最初的催化剂床温度550℃下降至525℃。空速和烃与催化剂比率的改变导致根据实施例1制备的改性CuO/H-ZSM-5催化剂的热中性反应。
初始催化剂床温度也影响改性H-ZSM-5催化剂的发热。参考图6,提供了随着反应时间的进行催化剂床温度曲线的比较,具有不同的初始催化剂床温度。使用氮气作为稀释剂,在588℃和WHSV为8.4hr-1下进行反应。反应参数与图5相同,但初始催化剂床温度从550℃升至588℃。随着初始催化剂床温度的增加,根据实施例1制备的改性CuO/H-ZSM-5催化剂最初产生更多热量,导致催化剂床温度从588℃升至超过625℃。相反,改性的CuO/H-ZSM-5催化剂在550℃的初始催化剂床温下反应,导致催化剂床温度稳定在550℃,没有明显的峰值。因此,在这些反应条件下在较高催化剂床温下产生的热量足以为所需的烃裂化过程补充热量。在这些反应条件下,可以在550℃达到热中性过程,并且在这些条件下可以在588℃达到热正性过程。
随后的实验数据是用根据实施例1、3和4制备的催化剂以及未改性H-ZSM-5催化剂在CREC(Western Ontario大学化学反应器工程中心)提升管模拟器批处理装置中获得的。CREC提升管模拟器批处理装置是一种间歇式反应器,可以接近再现工业连续“提升管”和“下行管”装置的反应条件,从而可以经济有效地研究和开发新的催化工艺。CREC提升管模拟器批处理装置由Reactor Engineering and Catalytic Technologies Inc.(加拿大安大略伦敦市)独家许可商业化。用固定在0.4g的反应器催化剂负载和5秒(s)的反应物停留时间进行裂化反应。另外,所有测试均在550℃下进行,催化剂与油的比率为0.7,停留时间为5秒。
在相同工艺参数下在CREC提升管模拟器批处理装置中测试实施例1、3和4以及未改性的H-ZSM-5催化剂允许直接比较实施例1、3和4的改型与未改性的H-ZSM-5催化剂。随后在表1中提供了每种样品的进料烃转化率以及C2和C3产率百分比。如前所述,己烷是实验装置的原料烃。转化率和产率百分比基于重量百分比。具体而言,己烷转化率如式[1]提供,单个产物的收率如式[2]提供。
表1
在表1中提供的CREC提升管模拟器批处理装置中实施例1、3和4以及未改性的H-ZSM-5催化剂的测试结果表明,通过改性H-ZSM-5催化剂,乙烯和丙烯等轻质烯烃的产率提高。另外,即使具有20%的金属氧化物负载量,如实施例1、3和4,烃进料的总转化率的损害也不显着。实施例1的铜改性催化剂显示出最高的烯烃产率增加,其次是钴和铬。
现在应理解,描述了用于烃裂化的发热催化剂的制备方法的各个方面,并且这些方面可以与各种其他方面结合使用。
在第一方面,本发明提供了制备用于烃裂化的发热催化剂的方法。该方法包括提供至少一种丝光沸石骨架反转(MFI)沸石催化剂,其具有15或更高的Si/Al摩尔比,提供至少一种金属氧化物前体;将至少一种金属氧化物前体分散在MFI沸石催化剂的微结构内,并煅烧具有分散在MFI沸石催化剂的微结构内的至少一种金属氧化物前体的发热催化剂,以原位形成至少一种金属氧化物。此外,MFI沸石催化剂与金属氧化物的比例以重量计在50:50至95:5的范围内。
在第二方面,本发明提供了第一方面的方法,其中所述至少一种金属氧化物前体通过湿浸渍、沉淀、电解沉积、沉积-沉淀、化学气相沉积和火焰喷雾热解中的至少一种分散在MFI沸石催化剂的微结构内。
在第三方面,本发明提供第一或第二方面的方法,其中所述至少一种金属氧化物是铁、铜、锌、铬、钼、钒、铈、锰、铋、银、钴、钒、锆、钨、镁的氧化物中的至少一种及其组合。
在第四方面,本发明提供第三方面的方法,其中所述至少一种金属氧化物包括氧化铜。
在第五方面,本发明提供第一至第四方面中任一方面的方法,其中金属氧化物前体是硝酸金属盐的水合物。
在第六方面,本发明提供第一至第五方面中任一方面的方法,其中金属氧化物前体为硝酸铜三水合物(Cu(NO3)2·3H2O)、硝酸钴(II)六水合物(Co(NO3)2·6H2O)或硝酸铬(III)九水合物(Cr(NO3)3·9H2O)。
在第七方面,本发明提供第一至第六方面中任一方面的方法,其中将金属氧化物前体分散在MFI沸石催化剂的微结构内包括将金属氧化物前体溶解在水中并逐滴添加到MFI沸石中。
在第八方面,本发明提供第一至第七方面中任一方面的方法,其中所述至少一种金属氧化物化学键合到MFI沸石催化剂的微结构上。
在第九方面,本发明提供了第七方面的方法,其中MFI沸石催化剂是平均粒度为5至850纳米的粉碎的ZSM-5催化剂。
在第十方面,本发明提供了第九方面的方法,其中ZSM-5催化剂是H-ZSM-5催化剂。
在第十一方面,本发明提供了第一至第十方面中任一方面的方法,其中煅烧发热催化剂是在空气中在400℃至800℃下进行足够的时间以将金属氧化物前体原位转化为金属氧化物。
在第十二方面,本发明提供第一至第十一方面中任一方面的方法,其中发热催化剂还包含促进剂。
在第十三方面,本发明提供了第十二方面的方法,其中所述促进剂是碱金属、碱土金属、稀土金属、过渡金属、磷及其组合中的至少一种。
在第十四方面,本发明提供了一种在烃裂化过程中使用发热催化剂的方法。该方法包括提供催化剂床反应器,将烃进料引入催化剂床反应器,和裂化烃进料以产生裂化产物。催化剂床反应器包括设置在催化剂床反应器中的发热催化剂的催化剂床。发热催化剂包括至少一种丝光沸石骨架反转(MFI)沸石催化剂,其具有15或更大的Si/Al摩尔比,和至少一种分散在MFI沸石催化剂的微结构内的金属氧化物。
在第十五方面,本公开提供第十四方面的方法,其中催化剂床反应器包含流化床反应器或固定床反应器。
在第十六方面,本发明提供了第十四方面至第十五方面中任一方面的方法,其中催化剂床反应器是固定床反应器,并且发热催化剂的催化剂床包括在一层MFI沸石催化剂之前设置的一层发热催化剂,在一层MFI沸石催化剂之后设置的一层发热催化剂,或在至少两层MFI沸石催化剂之间设置的至少一层发热催化剂。
在第十七方面,本发明提供了第十四方面至第十六方面中任一方面的方法,其中所述至少一种金属氧化物化学键合到MFI沸石催化剂的微结构上。
在第十八方面,本发明提供了第十四方面至第十七方面中任一方面的方法,其中发热催化剂还包含促进剂。
在第十九方面,本发明提供了第十四方面至第十八方面中任一方面的方法,其中所述促进剂是碱金属、碱土金属、稀土金属、过渡金属、磷及其组合中的至少一种。
在第二十方面,本发明提供了第十四方面至第十九方面中任一方面的方法,其中MFI沸石催化剂是ZSM-5催化剂。
在第二十一方面,本发明提供了第二十方面的方法,其中ZSM-5催化剂是H-ZSM-5催化剂。
对于本领域技术人员显而易见的是,在不脱离所要求的主题的精神和范围的情况下,可以对所描述的实施方案进行各种修改和变化。因此,希望本说明书覆盖本文中所描述的各种实施方案的修改和变化,其条件是,此类修改和变化落在所附权利要求及其等效物的范围内。
贯穿本公开,提供了范围。可以设想,还包含范围涵盖的每个离散值。另外,可以同样设想由明确公开的范围涵盖的每个离散值形成的范围。
Claims (20)
1.制备用于烃裂化的发热催化剂的方法,所述方法包括:
提供至少一种丝光沸石骨架反转(MFI)沸石催化剂,其具有15或更高的Si/Al摩尔比;
提供至少一种金属氧化物前体;
将至少一种金属氧化物前体分散在MFI沸石催化剂的微结构中;
煅烧具有分散在MFI沸石催化剂的微结构内的至少一种金属氧化物前体的发热催化剂,以原位形成至少一种金属氧化物,
其中MFI沸石催化剂与金属氧化物的比例以重量计为50:50至95:5。
2.根据权利要求1所述的方法,其中所述至少一种金属氧化物前体通过湿浸渍、沉淀、电解沉积、沉积-沉淀、化学气相沉积和火焰喷雾热解中的至少一种分散在MFI沸石催化剂的微结构内。
3.根据权利要求1所述的方法,其中所述至少一种金属氧化物是铁、铜、锌、铬、钼、钒、铈、锰、铋、银、钴、钒、锆、钨、镁的氧化物及其组合中的至少一种。
4.根据权利要求3所述的方法,其中所述至少一种金属氧化物包括氧化铜。
5.根据权利要求1所述的方法,其中所述金属氧化物前体是硝酸金属盐的水合物。
6.根据权利要求5所述的方法,其中所述金属氧化物前体为硝酸铜三水合物(Cu(NO3)2·3H2O)、硝酸钴(II)六水合物(Co(NO3)2·6H2O)或硝酸铬(III)九水合物(Cr(NO3)3·9H2O)。
7.根据权利要求5所述的方法,其中将金属氧化物前体分散在MFI沸石催化剂的微结构内包括将金属氧化物前体溶解在水中并逐滴添加到MFI沸石中。
8.根据权利要求1所述的方法,其中所述至少一种金属氧化物化学键合到MFI沸石催化剂的微结构上。
9.根据权利要求7所述的方法,其中MFI沸石催化剂是平均粒度为5至850纳米的粉碎的ZSM-5催化剂。
10.根据权利要求9所述的方法,其中ZSM-5催化剂是H-ZSM-5催化剂。
11.根据权利要求1所述的方法,其中煅烧发热催化剂是在空气中在400℃至800℃下进行足够的时间以将金属氧化物前体原位转化为金属氧化物。
12.根据权利要求1所述的方法,其中所述发热催化剂还包含促进剂。
13.根据权利要求12所述的方法,其中所述促进剂是碱金属、碱土金属、稀土金属、过渡金属、磷及其组合中的至少一种。
14.在烃裂化过程中使用发热催化剂的方法,所述方法包括:
提供催化剂床反应器,
其中催化剂床反应器包括设置在催化剂床反应器中的发热催化剂的催化剂床,
所述发热催化剂包括:
至少一种具有Si/Al摩尔比为15或更大的丝光沸石骨架反转(MFI)沸石催化剂,和
至少一种分散在MFI沸石催化剂的微结构中的金属氧化物;
将烃进料引入所述催化剂床反应器;和
裂解所述烃进料以产生裂化产物。
15.根据权利要求14所述的方法,其中催化剂床反应器包含流化床反应器或固定床反应器。
16.根据权利要求15所述的方法,其中催化剂床反应器是固定床反应器,并且发热催化剂的催化剂床包括在一层MFI沸石催化剂之前设置的一层发热催化剂,在一层MFI沸石催化剂之后设置的一层发热催化剂,或在至少两层MFI沸石催化剂之间设置的至少一层发热催化剂。
17.根据权利要求14所述的方法,其中所述至少一种金属氧化物化学键合到MFI沸石催化剂的微结构上。
18.根据权利要求14所述的方法,其中所述发热催化剂还包含促进剂。
19.根据权利要求18所述的方法,其中所述促进剂是碱金属、碱土金属、稀土金属、过渡金属、磷和它们的组合中的至少一种。
20.根据权利要求14所述的方法,其中所述MFI沸石催化剂是ZSM-5催化剂。
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