CN1111518C - 重芳烃的加工方法 - Google Patents
重芳烃的加工方法 Download PDFInfo
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- CN1111518C CN1111518C CN98805980A CN98805980A CN1111518C CN 1111518 C CN1111518 C CN 1111518C CN 98805980 A CN98805980 A CN 98805980A CN 98805980 A CN98805980 A CN 98805980A CN 1111518 C CN1111518 C CN 1111518C
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- benzene
- zeolite
- toluene
- aromatic hydrocarbons
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- 238000000034 method Methods 0.000 title claims abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 141
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000010457 zeolite Substances 0.000 claims abstract description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 43
- 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 43
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 29
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- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 5
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- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZKRXZOLGLXXMEA-UHFFFAOYSA-N dioxosilane zirconium Chemical compound [Zr].[Si](=O)=O ZKRXZOLGLXXMEA-UHFFFAOYSA-N 0.000 description 2
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 2
- 229910003452 thorium oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WGSMMQXDEYYZTB-UHFFFAOYSA-N 1,2,4,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C=C1C.CC1=CC(C)=C(C)C=C1C WGSMMQXDEYYZTB-UHFFFAOYSA-N 0.000 description 1
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- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 229910001649 dickite Inorganic materials 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
将重芳烃加料物转变成轻质芳族产物如苯,方法是将C9+芳烃馏份和甲苯在下列催化剂上接触,所述催化剂包括含有约束指数为0.5-3的沸石和氢化组分的第一催化剂组合物和含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石的第二催化剂组合物,由此降低或消除了共沸物的量。
Description
本发明涉及将重芳烃,特别是C9+芳烃,转变为轻质芳族产物。更具体地说,本发明涉及有改进纯度的苯的生产。
苯和二甲苯的来源是催化重整产物,催化重整产物是通过将石脑油与氢混合,然后使该混合物与强的加氢/脱氢催化剂,如在适当的酸性载体,如卤素处理的氧化铝上的铂接触而制备的。通常,从重整产物中分离出C6-C8级分,然后用对芳烃或脂族烃有选择性的溶剂萃取以分离这两种化合物,得到一种含脂族烃较少的芳族化合物的混合物。这种芳族化合物的混合物通常含有苯、甲苯和二甲苯(BTX)以及乙苯。
炼油厂也集中于通过C9+芳烃和甲苯在含贵金属的沸石催化剂上进行烷基转移反应来生产苯和二甲苯。在C9+芳烃和甲苯在含贵金属的催化剂上进行烷基转移反应生产高价值石油化学品时,在头几个月的物流中通常会产生副产物饱和化合物。这些副产物饱和化合物,称之为共沸物,可以在如高价值石油化学品同样的温度范围沸腾,这就使得高纯度的高价值石油化学品的分离更困难。例如,工业级的苯产品的纯度必须超过99.85%。但是,在烷基转移反应产物蒸馏后的最初苯产品的纯度通常仅为99.2-99.5%。这是由于存在共沸物,如甲基环戊烷、环己烷、2,3-二甲基戊烷、二甲基环戊烷和三甲基己烷的缘故。所以,为了进一步提高苯产品的纯度到所需水平,通常需要一个附加的萃取步骤。
鉴于在得到高纯的苯石油化学品时由于C9+芳烃和甲苯在含贵金属的沸石催化剂上进行烷基转移反应时形成的共沸物造成的困难,所以就有必要降低烷基转移反应时生成的共沸物量。降低烷基转移反应时生成的共沸物量的一个优点是,在烷基转移反应的产物蒸馏后就可得到高纯的苯产物,而不需要附加的萃取步骤,因而可以减少为得到纯度至少为99.85%的苯产物所需的反应步骤数目。
本发明一般地是涉及将重芳烃转变为轻质芳族产物的方法。更具体地说,本发明是涉及一种在重芳烃,特别是C9+芳烃,和甲苯进行烷基转移反应生成苯和二甲苯时,减少生成的共沸物量的方法。
本发明涉及一种将含有C9+芳烃和甲苯的加料物转变成含有苯和二甲苯的方法,其中该方法包括将含有C9+芳烃和甲苯的加料物在烷基转移反应的条件下与下列催化剂接触的步骤,所述催化剂包括(1)含有约束指数为0.5-3的沸石和氢化组分的第一催化剂组合物,和(2)含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石的第二催化剂组合物,生成包括苯和甲苯的烷基转移反应产物,并且不需要萃取步骤。
图1示出了该烷基转移反应的典型的工艺流程图。
本发明一般地是涉及将重芳烃转变为轻质芳族产物的方法。
更具体地说,本发明是涉及一种在重芳烃,特别是C9+芳烃,和甲苯进行烷基转移反应生成含有苯和二甲苯的烷基转移反应产物时,减少生成的共沸物量的方法。通过从烷基转移反应产物中蒸馏出苯,可以得到纯度至少为99.85%的苯产物,而不需要萃取步骤。
本发明的特征在于,是通过采用一种含有约束指数为0.5-3的沸石和氢化组分的第一催化剂组合物,和一种含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石的第二催化剂组合物,使在重芳烃和甲苯进行烷基转移反应生成苯和甲苯时减少或消除共沸物的产生,从而达到生产高纯苯的目的。测定沸石约束指数的方法完整地描述于美国专利4016218中。
在重芳烃和甲苯进行烷基转移反应生成苯和甲苯时减少或消除共沸物产生的优点是取消了通常为得到高纯苯所需要的萃取步骤。第一催化剂组合物
本发明的反应是通过与约束指数为0.5-3的沸石接触进行催化。特别有用的沸石包括沸石MCM-22、PSH-3、SSZ-25、ZSM-12和沸石β。
沸石β更具体地描述于美国专利Re.28341(原始美国专利是3308069)。
ZSM-12更具体地描述于美国专利3832449。
SSZ-25描述于美国专利4954325。
PSH-3描述于美国专利4439409。
沸石MCM-22,或简称为“MCM-22”,更具体地描述于美国专利4954325。
也希望将另一种能耐温和耐受本发明使用的其他条件的材料加进沸石中。这种材料包括活性和非活性材料及合成的或天然存在的沸石,以及无机材料如粘土、硅石和/或金属氧化物如氧化铝。无机材料既可以是天然存在的,或以凝胶状的沉淀物或包括二氧化硅和金属氧化物的混合物的凝胶形式。
采用与沸石在一起的材料,也即是与沸石相结合的或在沸石合成时存在的材料,该材料本身是有催化活性的,可以改变催化剂组合物的转化率和/或选择性。非活性的材料适合作为稀释剂以控制转化率的大小,因而可以经济地和顺序地得到烷基转移产物,不需采用控制反应速率的其他方法。这些可以加入的有催化活性或无催化活性的材料,例如天然存在的粘土,如膨润土和高岭土,可以改进催化剂组合物在工业操作条件下的抗碎强度。希望提供的催化剂组合物具有良好的抗碎强度,因为在工业使用时,要求能防止催化剂组合物碎裂成粉末状的材料。
可以与本文的沸石复合作为催化剂组合物粘接料的天然存在粘土,包括蒙脱土和高岭土类,这类粘土包括变膨润土,高岭土普通已知有Dixie、McNamee、Georgia和Florida粘土或主要矿物成分是埃硌石、高岭土、地开石、珍珠陶土或富硅高岭土的其他粘土。这些粘土可以以原生态如最初被开采的状态或初步进行煅烧、酸处理或化学改性后的状态使用。
除了前述的材料外,沸石还可以与多孔的基体粘接料复合,如选自以下的无机氧化物:二氧化硅、氧化铝、氧化锆、氧化钛、氧化钍、氧化铍、氧化镁和其组合如二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-氧化钛以及三元组合物如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。也是有利的是,提供至少一部分以胶体形式的前述多孔的基体粘接料,以便进行催化剂组合物的挤出操作。
沸石通常是与粘接料或基质材料混合的,所以最终的催化剂组合物含有5-90%(重量),优选10-60%(重量)的粘接料或基质材料。
第一催化剂组合物的沸石是与至少一种氢化组分,如选自元素周期表(CAS版,1079)VIII族的金属,组合使用的。有用的氢化组分的具体例子是铁、钌、锇、镍、钴、铑、铱,或贵金属如铂或钯。
氢化组分的量根据氢化活性和催化功能性之间的平衡来选择。当使用活性最高的金属如铂来代替不具有如此强氢化活性的钯时,氢化组分需要的量少些。通常,用量低于10%(重量),经常不超过1%(重量)。
氢化组分进入第一催化剂组合物可以通过共结晶,一定程度地交换存在于结构中的IIIA族元素,例如铝,进入组合物,浸渍在组合物中,或与沸石和粘接料混合。这种组分可以浸渍在沸石之中或之上,例如,在铂的情况下,将沸石用含有含铂金属离子的溶液处理。适合的用铂浸渍催化剂的铂化合物包括氯铂酸、氯化亚铂和各种含铂胺配合物的化合物,如Pt(NH3)4Cl2H2O。
替换地,氢化组分的化合物可以在沸石与粘接料复合时,或在沸石和粘接料通过挤出或造粒的方法成型为颗粒之后加到沸石中。
在用氢化组分处理后,催化剂组合物通常要进行干燥,方法是在温度150-320°F,更优选230-290°F,和压力0-15psia下加热催化剂组合物至少1分钟,通常不长于24小时。其后,将催化剂组合物在在干气流中,如空气或氮气,和温度500-1200°F下煅烧1-20小时。进行煅烧的压力优选为15-30psia。
使用之前催化剂组合物要进行蒸汽处理使催化剂组合物的芳烃氢化活性降到最低。在蒸汽加工时,催化剂组合物通常与5-100%的蒸汽在温度至少500-1200°F,压力14-360psia下接触至少1小时,特别是1-20小时。第二催化剂组合物
本发明的第二催化剂组合物含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石。特别有用的沸石包括ZSM-5,如美国专利3702886所述,或其质子或氢的形式,即HZSM-5。第二催化剂组合物的沸石能够在1分钟或以上,优选2分钟或以上的较短接触时间内将不需要的C6和C7的非芳烃转化。
第二催化剂组合物的沸石可以与多孔的基体粘接料复合,如选自以下的无机氧化物:二氧化硅、氧化铝、氧化锆、氧化钛、氧化钍、氧化铍、氧化镁和其组合如二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-氧化钛以及三元组合物如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。也是有利的是,提供至少一部分以胶体形式的前述多孔的基体粘接料,以便进行催化剂组合物的挤出操作。
沸石通常是与粘接料或基质材料混合,以致最终的催化剂组合物含有5-90%(重量),优选10-60%(重量)的粘接料或基质材料。
第二催化剂组合物可以占烷基转移反应区中第一和第二催化剂组合物总重量的1-20%(重量),优选10-15%(重量)。例如,在反应器底部,第二催化剂组合物可以代替一部分第一催化剂组合物,因而在同一反应器中,第一催化剂组合物存在于第一催化剂床上,第二催化剂组合物存在于第二催化剂床上。替换地,第一催化剂组合物可以存在于第一反应器中,第二催化剂组合物可以存在于第二反应器中。加料物
用于本发明工艺的C9+芳烃通常含有一种或几种含至少9个碳原子的芳族化合物如例如三甲基苯、二甲苯和二乙苯等。具体的C9+芳族化合物包括米(1,3,5-三甲基苯)、杜烯(1,2,4,5-四甲基苯)、连三甲基苯(1,2,3-三甲基苯)、假枯烯(1,2,4-三甲基苯)、1,2-甲基乙基苯、1,3-甲基乙基苯、1,4-甲基乙基苯、丙基取代的苯、丁基取代的苯、二甲基-乙苯的异构体等。
C9+芳烃适合的来源是任何富产芳烃的炼油厂工艺来的任何C9+馏份。这种芳烃馏份含有大部分是C9+芳烃,例如至少80%(重量)的C9+芳烃,其中优选至少80%(重量),更优选90%(重量)以上的烃类是C9-C12烃。典型的可用炼油厂馏份包括催化重整产物、FCC(流化床催化裂解)石脑油或TCC(蓄热器催化裂解)石脑油。
甲苯的来源可来自芳烃萃取装置或任何市售产品。
典型地,加入烷基转移反应区的物料含有C9+芳烃和甲苯。加料物也可包括循环的/未反应的甲苯和通过烷基转移反应本身的流出产物蒸馏得到的C9+芳烃。通常,甲苯占整个加料物的40-90%(重量),优选50-70%(重量)。C9+芳烃占加入烷基转移反应区的整个加料物的10-60%(重量),优选30-50%(重量)。烃转化工艺
该工艺可以在任何适当的反应器中进行,所述反应器包括径向流反应器、固定床反应器、连续下流式反应器或流化床反应器。烷基转移反应的温度典型为650-950°F,优选为750-850°F;压力为100-600psia,优选为200-500psia;氢和烃的摩尔比为1-5,优选1-3。在第一催化剂组合物上的加料速率为1.0-7.0WHSV(重量时空速度),优选为2.5-4.5WHSV;在第二催化剂组合物上的加料速率为5.0-100.0WHSV,优选为15.0-35.0WHSV。烷基转移反应条件足以使重芳烃加料物转变成含大部分是C6-C8的芳族化合物如苯、甲苯和二甲苯,特别是苯和二甲苯的产物。
下面参考图1的简化流程图进行阐述。C9+芳烃物流与甲苯和氢一起经由管线10导入含有第一和第二催化剂组合物的反应器12。反应器保持在足以使甲苯和甲基芳烃(甲苯、二甲苯、三甲基苯和四甲基苯)通过烷基转移反应趋近热力学平衡的条件下。反应器12的产物经由管线14排出进入氢分离器16,从氢分离器分离出的氢经由管线18循环到反应器12。然后物料经由管线20进入稳定器部分22,用已知的方法除去C5可燃气。此后,产物在为分馏成苯、甲苯和二甲苯物流的分馏器24、26和28中分别分馏成苯、甲苯和二甲苯物流。含有未反应的C9+加料物和所有重芳烃的剩余产物被分离成C9芳烃物流30和C10+芳烃物流29。物流30循环回到反应器加料物中,或从工艺中取出,或两种情况相结合(部分循环)。C10芳烃物流29适合作为汽油掺混物或其他产品如溶剂。
实施例
氧化铝粘结的ZSM-5催化剂用高硅氧玻璃稀释并装载到外经为3/8英寸的反应器中,和在750°F的氮气流下干燥。将氢气流代替氮气流,并将C9+芳烃、甲苯和氢的混合物流经含约束指数0.5-3的沸石的催化剂上后得到的产物,以不同的流量导入反应器,同时保持氢和烃的摩尔比为3/1,和压力为350psia。用150m带有氢载气的petrocol柱对反应器的排出物进行色谱分析,重要组分归一化的数据列于表1。蒸馏苯的纯度根据这个归一化表的数据按下面的方程计算,其中的加权因子是用模拟科学公司(Simulation Sciences)的ProvisionTM软件进行模拟蒸馏得出的。
蒸馏苯的纯度=100×苯/(苯+a+b+c+d)其中:
a=0.1*C6-链烷烃
b=0.7*甲基环戊烷
c=环己烷
d=C7环烷烃(二甲基环戊烷、甲基环己烷等)
WHSV TransPlus 14 19 29 29 30
产物温度(°F) 750 750 750 750 797 774归一化后%2,3-二甲基丁烷 0.014 0.000 0.000 0.000 0.000 0.000环戊烷 0.093 0.000 0.012 0.012 0.000 0.0002-甲基戊烷 0.108 0.036 0.049 0.043 0.031 0.0423-甲基戊烷 0.063 0.022 0.032 0.023 0.019 0.026正己烷 0.070 0.014 0.027 0.027 0.011 0.017甲基环戊烷 0.231 0.012 0.038 0.064 0.000 0.031苯 99.210 99.833 99.762 99.727 99.900 99.807环己烷 0.048 0.028 0.023 0.025 0.000 0.0161,顺3-二甲基环戊烷 0.017 0.000 0.000 0.000 0.000 0.0001,反3-二甲基环戊烷 0.015 0.000 0.000 0.000 0.000 0.0001,反2-二甲基环戊烷 0.020 0.000 0.000 0.000 0.000 0.000甲基环己烷 0.110 0.055 0.058 0.080 0.039 0.061总量 100.000 100.00 100.00 100.00 100.00 100.00苯 99.210 99.833 99.762 99.727 99.900 99.807a 0.035 0.007 0.012 0.010 0.006 0.008b 0.161 0.008 0.026 0.044 0.000 0.021c 0.048 0.028 0.023 0.025 0.000 0.016d 0.163 0.055 0.058 0.080 0.039 0.061估算的蒸馏苯的纯度 99.591 99.902 99.881 99.840 99.955 99.893
由表1可见,在恒定的温度和压力(750°F,350psia)下,在较低WHSV时由于增加了非芳烃组分的转化率,苯的纯度提高。随着WHSV的增加,甲基环戊烷和甲基环己烷转化率的下降,成为蒸馏苯不纯度的主要贡献者。但是,甚至在29WHSV,蒸馏苯的纯度都已被提高到能满足99.85%的规定。同样,升高温度造成这些甲基环烷烃的浓度更低,使得蒸馏苯的纯度大大提高。此外,增加温度也使环己烷的浓度显著降低。
Claims (8)
1.一种将C9+芳烃转变为轻质芳族产物的方法,该方法包括将(i)C9+芳烃和(ii)甲苯或苯在烷基转移反应的条件下在下列催化剂上反应的步骤,所述催化剂包括含有约束指数为0.5-3的沸石和氢化组分的第一催化剂组合物和含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石的第二催化剂组合物,其中,第二催化剂组合物占第一和第二催化剂组合物总重量的1-20重量%,生成包括(i)苯或甲苯和(ii)二甲苯的烷基转移反应产物。
2.一种生产苯的方法,包括以下的步骤:
(a)将(i)C9+芳烃和(ii)甲苯或苯在烷基转移反应的条件下在下列催化剂上反应,所述催化剂包括含有约束指数为0.5-3的沸石和氢化组分的第一催化剂组合物和含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石的第二催化剂组合物,其中,第二催化剂组合物占第一和第二催化剂组合物总重量的1-20重量%,生成包括(i)苯或甲苯和(ii)二甲苯的产物流;和
(b)从所述产物流中蒸馏出苯或甲苯,得到苯或甲苯产物。
3.根据权利要求2的方法,其中步骤(b)的苯产物的纯度至少为99.85%。
4.根据权利要求3的方法,其中步骤(b)的苯产物的纯度至少为99.85%,不需要附加的萃取步骤。
5.根据权利要求1的方法,其中第一催化剂组合物的氢化组分至少是一种选自元素周期表VIII族的金属,并且第一催化剂组合物的沸石是选自MCM-22、PSH-3、SSZ-25、ZSM-12和沸石β。
6.根据权利要求5的方法,其中第二催化剂组合物的沸石是ZSM-5。
7.根据权利要求1的方法,其中烷基转移反应条件包括温度为650-950°F,压力为100-600psia,氢和烃的摩尔比为1-5。
8.一种将C9+芳烃转变为轻质芳族产物的方法,该方法的步骤包括(a)将(i)C9+芳烃和(ii)甲苯或苯在烷基转移反应的条件下在含有第一催化剂组合物的第一催化剂床上反应,所述第一催化剂组合物含有约束指数为0.5-3的沸石和氢化组分,生成一个中间产物流,和(b)将所述中间产物流通过含有第二催化剂组合物的第二催化剂床,所述第二催化剂组合物含有约束指数为3-12和二氧化硅与氧化铝的比至少为5的中等孔径沸石,生成包括(i)苯或甲苯和(ii)二甲苯的最终烷基转移反应产物。
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CA2290694C (en) | 2008-07-29 |
EP0988265A1 (en) | 2000-03-29 |
TW402587B (en) | 2000-08-21 |
PT988265E (pt) | 2002-11-29 |
DE69807476D1 (de) | 2002-10-02 |
AU8070598A (en) | 1998-12-30 |
EP0988265B1 (en) | 2002-08-28 |
BG103960A (en) | 2000-06-30 |
DE69807476T2 (de) | 2003-01-02 |
CN1259930A (zh) | 2000-07-12 |
ES2180181T3 (es) | 2003-02-01 |
AU738979B2 (en) | 2001-10-04 |
ID24255A (id) | 2000-07-13 |
US5942651A (en) | 1999-08-24 |
PL337778A1 (en) | 2000-09-11 |
RU2183611C2 (ru) | 2002-06-20 |
EP0988265A4 (en) | 2000-10-04 |
CA2290694A1 (en) | 1998-12-17 |
JP2002504946A (ja) | 2002-02-12 |
KR100534062B1 (ko) | 2005-12-07 |
KR20010013333A (ko) | 2001-02-26 |
JP4021943B2 (ja) | 2007-12-12 |
WO1998056741A1 (en) | 1998-12-17 |
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