CN1139659A - 使用含有改性的硅铝磷酸盐分子筛的催化剂的c8芳族化合物异构化 - Google Patents
使用含有改性的硅铝磷酸盐分子筛的催化剂的c8芳族化合物异构化 Download PDFInfo
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- CN1139659A CN1139659A CN96105444A CN96105444A CN1139659A CN 1139659 A CN1139659 A CN 1139659A CN 96105444 A CN96105444 A CN 96105444A CN 96105444 A CN96105444 A CN 96105444A CN 1139659 A CN1139659 A CN 1139659A
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- molecular sieve
- catalyst
- isomerization
- platinum
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
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- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- 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
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Abstract
通过将一种非平衡态C8芳族化合物进料混合物在氢存在下与含铂族组分和SM-3酸性结晶硅铝磷酸盐分子筛的组合的催化剂在C8芳族化合物异构化条件下接触使该进料选择性异构化,得到富含对二甲苯的异构化产品。SM-3分子筛的表面富含骨架硅,从而导致对二甲苯的收率比现有技术方法更大。
Description
本发明涉及一种新的烷基芳烃的异构化方法,更具体地说,涉及使用具有精确限定的组成的分子筛催化剂异构化C8芳烃以提高二甲苯收率。
具有各种组成和结构的分子筛业已在现有技术中公开用作烃类转化的催化剂。最为公知的是由共顶的AlO2和SiO2四面体形成的结晶硅铝酸盐沸石。这些沸石的一般特征是具有尺寸均匀的开孔、显著的离子交换能力和能可逆地解吸分散在结晶的整个内部空隙中的吸附相,而不会置换任何构成永久晶体结构的原子。沸石的通常特征在于临界的,一般是最小的二氧化硅/氧化铝比。
新近已公开了一类含有铝(AlO2)、磷(PO2)和至少一种附加元素EL(ELO2)的骨架四面体单元(TO2)的有用的非沸石型分子筛。“非沸石型分子筛”包括公开于US-A-4793984中的“ELAPSO”分子筛和公开于US-A-4440871中的“SAPO”分子筛。上述专利通常提出了宽范围的骨架金属浓度,例如在US-A-4440871中硅的摩尔分数可取决于其他骨架元素而为0.01-0.98,优选范围是0.02-0.25摩尔分数。US-A-4943424公开了一种硅铝磷酸盐(Silicoaluminophosphate)分子筛,其特征在于该分子筛的表面和主体中P2O5与其表面和主体中氧化铝的比率、表面的硅含量以及其在脱蜡和氢化裂解中的用途。
US-A-4740650提出使用一种含至少一种非沸石型分子筛(优选为硅铝磷酸盐)的催化剂使二甲苯异构化。该专利未提出为本发明所用改性分子筛的一个特征的临界组分梯度(critical composi-tion gradient)。
用于C8芳族化合物的异构化的催化剂通常按加工与二甲苯异构体相关的乙苯的方式分类。乙苯不易异构化成二甲苯,但它通常在异构化装置中进行转化,因为通过超精馏或吸附将它从二甲苯中分离很昂贵。一种广泛使用的方法是使乙苯脱去烷基而主要形成苯,同时将二甲苯异构化成***衡态混合物。另一方法是在带氢化-脱氢官能团的固体酸催化剂存在下经过转化成环烷烃和从环烷烃再转化而使乙苯反应,从而形成二甲苯混合物。前一方法通常导致较高的乙苯转化率,因而降低循环到对二甲苯回收装置中的量并随之降低加工成本,但后一方法通过由乙苯形成二甲苯而提高二甲苯产率。根据后一方法,提高转化率,即,使乙苯以高转化率异构化成二甲苯的催化剂复合体和方法可显著改进生产二甲苯的经济状况。
本发明的主要目的是提供一种新的烷基芳烃的异构化方法。更具体地说,本发明涉及使用精确限定的分子筛催化剂异构化C8芳烃以提高二甲苯收率。
本发明基于如下发现:一种包含表面富含硅的SAPO分子筛的催化剂提高了烷基芳族化合物、尤其是C8芳族化合物异构化的转化率和选择性。
因此,本发明的一个主要实施方案涉及使用骨架表面富含硅的硅铝磷酸盐(SAPO)分子筛催化剂的烷基芳烃异构化方法。该方法包括使用该催化剂在异构化条件下使包含二甲苯和乙苯的非平衡态混合物的原料异构化,从而得到相对于该原料来说对二甲苯含量得以增加的产品。优选该含SAPO的催化剂包含铂族金属,尤其优选的成分是铂。最佳的催化剂复合体还包含一种无机氧化物粘结剂,通常为氧化铝和/或二氧化硅。
用于芳族化合物异构化方法的原料一般包含任何组合的通式为C6H(6-n)Rn(其中n为1-5的整数,R为CH3、C2H5、C3H7或C4H9)且包括其所有异构体的可异构化烷基芳烃,从而得到更有价值的烷基芳烃异构体。例如合适的烷基芳烃包括(但不限制本发明)邻二甲苯、间二甲苯、对二甲苯、乙苯、乙基甲苯、三甲基苯、二乙基苯、三乙基苯、甲基丙基苯、乙基丙基苯、二异丙基苯及其混合物。
含乙苯和二甲苯的C8芳族化合物混合物的异构化是本发明SAPO分子筛的一个特别优选的应用。通常,此类混合物的乙苯含量大约为5-50%(质量),邻二甲苯含量大约为0-35%(质量),间二甲苯含量大约为20-95%(质量),而对二甲苯含量大约为0-15%(质量)。优选上述C8芳族化合物包含一种非平衡态混合物,即至少一种C8芳族化合物异构体的存在浓度与异构化条件下的平衡浓度显著不同。该非平衡态混合物一般通过除去从芳族化合物生产方法得到的新鲜C8芳族化合物混合物中的对-和/或邻-二甲苯而制备。
烷基芳烃进料源可通过选择性分馏和蒸馏催化裂解或重整的烃而以单一组分或以某一沸程的馏分从来自各种炼油厂石油料流的合适馏分中得到。可异构化的芳烃不必浓缩;本发明可使含芳族化合物的料流如催化重整产品异构化,随后抽提或不抽提芳族化合物,从而生产出特定的二甲苯异构体,特别是生产出对二甲苯。C8芳族化合物进料可以含有非芳族烃,即环烷烃和链烷烃,其量在30%(质量)以内。然而,优选可异构化烃基本由芳烃组成,以确保从下游回收程序得到纯净产品。
根据本发明,烷基芳烃进料混合物,优选与氢气混合,在烷基芳烃异构化区与下述类型的催化剂接触。接触可使用固定床体系、移动床体系、流化床体系的催化剂或以间歇式操作进行。从有用催化剂磨耗损失的危险和更简单的操作来看,优选使用固定床体系。在该体系中,富氢气体与进料混合物由合适的加热装置预热到预期的反应温度,然后送入含有固定床催化剂的异构化区中。转化区可以是一个或多个其间具有合适装置的单独反应器,以确保在各区的入口处维持预期的异构化温度。反应物可以上向流、下向流或径向流方式与催化剂床接触,而且该反应物在与催化剂接触时可以为液相、液-汽混合相或汽相。
烷基芳族化合物进料混合物,优选C8芳族化合物的非平衡态混合物在合适的烷基芳族化合物异构化条件下与异构化催化剂接触。这些条件包括0℃至600℃或更高的温度,优选300-500℃。压力通常为101.3-10130 kPa(1-100大气压),优选低于5065kPa(50大气压)。在异构化区应含有足够的催化剂,以对烃料混合物提供0.1-30hr-1,优选0.5-10hr-1的液体时空速(LHSV)。烃料混合物最好以和氢气的混合物形式以0.5∶1-约25∶1或更高的氢/烃摩尔比反应。可存在其他惰性稀释剂如氮、氩和轻质烃。
用于从异构化区的反应器的流出物中回收异构化产品的具体方案似乎并不关键。一般来说,反应器流出物将被冷凝,而且通过石油接触脱气(flash separation)从中除去氢和轻质烃组分。然后将冷凝的液体产品分馏,除去轻质和/或重质副产物并得到异构化产品。在某些情形中,可通过选择性分馏从异构化产品中回收某些产品样本如邻二甲苯。通常通过结晶或选择性吸附或其结合对C8芳族化合物异构化得到的产品进行加工以选择性回收对二甲苯异构体。优选使用US-A-3201491的结晶硅铝酸盐进行选择性吸附。在优选的吸附回收法中的改进和替换在US-A-3626020、US-A-3696107、US-A-4039599、US-A-4184943、US-A-4381419和US-A-4402832中有描述。
在与乙苯/二甲苯混合物的加工有关的分离/异构化方法组合中,新鲜的C8芳族化合物进料与来自异构化反应区的含C8芳族化合物和环烷烃的异构化产品混合并供入对二甲苯分离区;将包含C8芳族化合物的非平衡态混合物的对二甲苯已减少的料流供入异构化反应区,在此C8芳族化合物异构体异构化为***衡态水平,从而得到异构化产品。在该操作方案中,未回收的C8芳族化合物异构体优选进行再循环以除去,直到它们或者转化为对二甲苯,或者因副反应而消耗。也可在对二甲苯分离之前对新鲜的C8芳族化合物进料或异构化产品或在两者的混合进行邻二甲苯的分离,优选通过分馏。
用于本发明的分子筛类型在US-A-4440871所述的硅铝磷酸盐分子筛的范围之内。所公开的硅铝磷酸盐分子筛为微孔结晶硅铝磷酸盐,具有PO2 +、AlO2 -和SiO2四面体单元的三维微孔骨架结构,而且其在无水时的主要试验化学组成为:
mR∶(SixAlyPz)O2其中“R”代表至少一个存在于晶体内的孔体系中的有机模板试剂;“m”表示每摩尔(SixAlyPz)O2存在的“R”的摩尔数,其值为0.02-0.3;“x”、“y”和“z”分别表示氧化物部分中存在的硅、铝和磷的摩尔分数,所述摩尔分数在US-A-4440871的图1所示三元图上的点A、B、C、D和E所确定的组成面积之内且对“x”、“y”和“z”为如下值:
摩尔分数点 x y zA 0.01 0.47 0.52B 0.94 O.01 0.05C O.98 0.01 0.01D 0.39 0.60 0.01E 0.01 0.60 0.39US-A-4440871的硅铝磷酸盐在此通常称为“SAPO”类或称为代表特定SAPO的“SAPO-n”(其中n为整数),如SAPO-11、SAPO-31、SAPO-40和SAPO-41。这里所指的特别优选的样品SAPO-11是其特征X-射线粉末衍射图至少含有下述d-间隔的硅铝磷酸盐:
SAPO-112θ d 相对强度9.4-9.65 9.41-9.17 m20.3-20.6 4.37-4.31 m21.0-21.3 4.23-4.17 vs21.1-22.35 4.02-3.99 m22.5-22.9(双重线) 3.95-3.92 m23.15-23.35 3.84-3.81 ms
本发明中具体使用改性的SAPO-11,它通称为“SM-3”。SM-3的组成和性能在US-A-4943424中有详细说明。SM-3在硅铝磷酸盐表面的P2O5对氧化铝的摩尔比为0.80或低于0.80,优选0.80-0.55;在SAPO主体中的P2O5对氧化铝的摩尔比为0.96或大于0.96,优选0.96-1;而在表面的二氧化硅对氧化铝的摩尔比大于在SAPO主体中的二氧化硅对氧化铝的摩尔比。优选SM-3以无水氧化物的摩尔比计具有如下组成:
mR∶Al2O3∶nP2O5∶qSiO2其中“R”代表至少一个存在于晶体内的孔体系中的有机模板试剂,“m”表示存在的“R”的摩尔数且其值应使每摩尔氧化铝存在0.02-2摩尔“R”,n值为0.96-1.1,优选0.96-1,而q值为0.1-4,优选0.1-1。该US-A-4943424专利因其公开了优选的SM-3的制备和性能而在此引作参考。
SM-3分子筛优选与一种便于形成催化剂颗粒的粘结剂以5-100%(质量)SM-3和0-95%(质量)粘结剂的比例复合,优选SM-3占该复合体的10-90%(质量)。该粘结剂应是多孔的吸附性载体,其表面积为25-500m2/g,组成均匀且对在烃转化法中使用的条件较耐火。术语“组成均匀”指载体未分层,其组成所特有的物种无浓度梯度且组成完全均匀。因此,若该载体为两种或更多种耐火材料的混合物,则这些材料的相对量在整个载体中将保持恒定和均匀。这意味着把业已通常用于烃转化催化剂中的载体材料包括在本发明范围内,这些载体材料如(1)耐火无机氧化物,如氧化铝、二氧化钛、氧化锆、氧化铬、氧化锌、氧化镁、氧化钍、氧化硼、二氧化硅-氧化铝、二氧化硅-氧化镁、氧化铬-氧化铝、氧化铝-氧化硼、二氧化硅-氧化锆等;(2)陶瓷材料、瓷料、铝土矿;(3)二氧化硅或硅胶,碳化硅,粘土及人工合成的和天然存在的硅酸盐,它们可用酸处理或不用酸处理,例如硅镁土(attapulgite clay)、硅藻土、漂白土、高岭土、硅藻土等;(4)天然存在的或人工合成的结晶沸石型硅铝酸盐,如氢形或已与金属阳离子交换的FAU、MEL、MFI、MOR、MTW(IUPAC委员会对沸石的命名);(5)尖晶石类如MgAl2O4、FeAl2O4、ZnAl2O4、CaAl2O4和其他具有式MO-Al2O3的类似化合物,其中M为2价金属;和(6)上述一种或多种材料的组合。
用于本发明的优选耐火无机氧化物为氧化铝。合适的氧化铝材料为公知为γ-、η-和θ-氧化铝的结晶氧化铝,其中γ-或η-氧化铝得到的结果最好。特别优选的氧化铝是在US-A-3852190和US-A-4012313中称为来自如齐格勒的US-A-2892858所述的齐格勒高级醇合成反应的副产物的氧化铝。为简化起见,这种氧化铝以后称“齐格勒氧化铝”。齐格勒氧化铝目前可从Vista ChemicalCompany以商标“Catapal”购得或从Condea Chemie GmbH以商标“Pural”购得。该材料是一种纯度极高的假勃姆石,它在高温煅烧之后产生高纯度γ-氧化铝。
另一优选粘结剂为无定形二氧化硅。优选的无定形二氧化硅为合成的白色无定形二氧化硅,它被归为湿法水合二氧化硅。这类二氧化硅由水溶液中的化学反应产生,它以超细的球形粒子从水溶液中沉淀出来。优选该二氧化硅的BET表面积为120-160m2/g。希望含有低含量的硫酸盐,优选低于0.3%(重量)。特别优选无定形二氧化硅粘结剂为非酸性,例如5%水悬浮液的PH呈中性或碱性(PH约7或7以上)。
催化剂复合体的优选形式为挤出物。公认的挤出方法最初涉及非沸石型分子筛在加入金属组分之前或之后与粘结剂和合适的胶化剂混合,以形成具有适当水分含量的均质糊或稠糊,从而可形成具有可接受的完整性以经受直接煅烧的挤出物。可挤出性通过分析该糊的水分含量来确定,优选水分含量为30-50%(重量)。然后通过一穿有许多孔的型板挤出该糊,并按本领域众所周知的技术切割空心粉型挤出物,从而产生颗粒。许多不同的挤出物形状是可能的,包括,但不局限于,圆柱形、三叶形(cloverleaf)、哑铃形以及对称和不对称多叶形(polylobates)。用本领域已知的方法将挤出物进一步成形为期望的形状如球形也在本发明的范围内。
该复合体的一种有利形状为球形,它由众知的油滴法(oil dropmethod)连续制造。优选本方法包括将分子筛、氧化铝溶胶和胶凝剂的混合物滴入保持在高温的油浴。混合物液滴在油浴中保持,直到凝固并形成水溶胶球。然后连续从油浴中取出这些球并独特地在油和氨溶液中进行特殊的老化处理,以进一步改善其物理性能。然后洗涤所产生的老化和胶凝的颗粒,在50-200℃的较低温度下干燥,并在450-700℃的温度下煅烧1-20小时。这一处理使水溶胶转化为相应的氧化铝基体。
铂族金属,包括铂、钯、铑、钌、锇和铱中的一种或多种,为本发明催化剂的优选组分。优选的铂族金属为铂。该铂族金属组分可以化合物如氧化物、硫化物、卤化物、氧硫化物等或以元素态金属形式或与该催化剂复合体的一种或多种其它成分混合存在于最终的催化剂复合体中。据信当所有铂族金属组分主要以还原态存在时得到的结果最好。铂族金属组分以元素态为准计算,通常占最终催化剂复合体的0.01-约2%(质量)。
铂族金属组分可以任何合适方式掺入催化剂复合体中。一种制备该催化剂的方法包括使用铂族金属的水可溶、可分解的化合物来浸渍煅烧过的分子筛/粘结剂复合体。另一方面,铂族金属化合物可在分子筛组分和粘结剂复合时加入。而另一种适当分配金属的方法是在复合挤出分子筛和粘结剂之前将金属组分与粘结剂复合。可按上述方法或其他已知方法使用的铂族金属的复合物包括氯铂酸、氯钯酸、氯铂酸铵、溴铂酸、三氯化铂、四氯化铂水合物、二氯羰基二氯化铂、氯化四氨铂、二硝基二氨基铂、四硝基铂(II)酸钠、氯化钯、硝酸钯、硫酸钯、氢氧化二氨钯(II)、氯化四氨钯(II)及类似物。
催化剂复合体含有其他已知可改变铂族金属组分效果的金属组分在本发明范围之内。此类金属改性剂可包括铼、锡、锗、铅、钴、镍、铟、镓、锌、铀、镝、铊及其混合物。可用本领域众知的任何方法将催化有效量的该金属改性剂掺到该催化剂中,使之呈均匀或层状分布。
本发明的催化剂复合体可含有一种卤素组分。该卤素组分可以是氟、氯、溴或碘或其混合物,优选氯。该卤素组分通常以与无机氧化物结合的状态存在。这一任选的卤素组分优选很好地分散于催化剂中且按元素态计占最终催化剂的大于0.2-15%(重量)。该卤素组分可以任何合适方式在该无机氧化物载体制备期间或在掺入其他催化组分之前、之时或之后掺入催化剂复合体中。
在100-320℃温度下干燥该催化剂复合体2-24或更多小时,并通常在400-650℃温度下、在空气中煅烧0.1-10小时,直到存在的金属化合物基本转化为氧化物形式。若需要,可通过在空气中引入卤素或含卤素化合物来调整该任选的卤素组分。
所得煅烧复合体最好进行基本无水的还原步骤,以确保得到任选金属组分的均匀且精细的分散体。这一还原步骤可任选地在本发明的操作设备中进行。在该步骤中优选使用基本纯净且干燥的氢气(即小于20体积ppm的H20)作为还原剂。该还原剂与催化剂在温度为200-650℃、接触时间为0.5-10小时的条件下接触,有效地将所有(VIII)族金属组分基本上还原成金属态。在某些情况中,所产生的还原的催化剂复合体也可用本领域已知方法有利地进行预硫化,从而在催化剂复合体中掺入以元素态为准计算为0.05-0.5%(质量)的硫。
制备用于在本发明方法中作异构化催化剂来进行试验的SM-3改性硅铝磷酸盐样品。SM-3按US-A-4943424制备且具有在US-A-4943424中所公开的特征。
不是本发明的未改性SAPO-11硅铝磷酸盐样品按US-A-4440871和如下所述制备。混合摩尔比例为50摩尔∶1.8摩尔的水和正磷酸(85%(质量)H3PO4),往该溶液中加入1.0摩尔氧化铝Versal 250,搅拌该混合物。然后以0.2摩尔的摩尔比例加入二氧化硅HiSil 250。定向剂(directing agent)为二正丙胺,加入比例为1.8摩尔。因此反应混合物的组成如下:
1.8(Pr2NH)∶0.2SiO2∶A12O3∶0.9P2O5∶50H2O加入占氧化物1.0%(质量)的SAPO-11种子并逐步将反应混合物加热至195℃且在该温度下保持12小时。离心回收固体反应产物,水洗并在空气中于100℃干燥。某些合成粉末按如下所述与氧化铝结合,然后在流动空气中在650℃下煅烧,以除去合成模板并使结合的催化剂样品的二氧化硅粘结剂凝固。不为本发明的未结合的对照物SAPO-11称为“对照物”。
实施例I
本发明的优点在一系列微反应器试验中得到证明。将未结合的催化剂以250mg的量装入微反应器中。在氢气氛下以可变温度将间二甲苯供入该反应器中。测量间二甲苯的转化率以及产品中对二甲苯与邻二甲苯的比率。SM-3硅铝磷酸盐与不是本发明的对照物SAPO-11的对比试验结果如下:
400℃ 500℃
SM-3 对照物 SM-3 对照物转化率,% 39.14 3.27 47.44 9.2对二甲苯/邻二甲苯, 1.24 0.73 1.06 1.6摩尔%
在两个温度下SM-3表现出显著优于对照催化剂的间二甲苯转化率。SM-3还将对二甲苯/邻二甲苯比率控制在平衡比率附近,而对照催化剂在低转化率下的二甲苯异构体比率剧烈变化。实施例II
将SM-3硅铝磷酸盐与氧化铝和氯化四氨铂以交替的铂含量复合,以帮助配制本发明的最佳催化剂。该复合体包含60%(质量)SM-3和40%(质量)氧化铝。将氯化四氨铂加入该复合体中以使铂含量以元素态计分别为0.28和0.14%(质量),煅烧该催化剂并还原。
使用中试用的连续反应器加工具有如下组成(质量%)的非平衡态C8芳族化合物进料来评价这些催化剂:乙苯 17%间二甲苯 58%邻二甲苯 25%将该进料以2hr-1的LHSV与100毫升催化剂接触,且氢/烃摩尔比为4。调节反应器温度以进行适当的转化。转化率表示为每一次通过乙苯的消失。C8芳族化合物损失主要是变成苯和甲苯,并产生较少量的轻质气体。结果如下:催化剂中Pt的质量% 0.28 0.14温度,℃ 386 380乙苯转化率,% 28 24.5C8芳族化合物损失,% 2.8 2.8实施例III
制备并测试催化剂样品,以说明铂位置对催化剂性能的影响。催化剂A按如下方式在实施例II中制备:将质量比为60∶40的硅铝磷酸盐和氧化铝与氯化四氨铂复合挤出,煅烧并还原,得到含0.28%(质量)Pt的催化剂。催化剂B按如下方式制备:首先将氧化铝与氯化四氨铂复合,然后与SM-3复合挤出,煅烧并还原,得到整体组成与催化剂A相同的催化剂。
使用中试用的连续反应器加工与实施例II相同的非平衡态C8芳族化合物进料来评价这些催化剂。该进料以2hr-1的LHSV和氢/烃摩尔比为4与100毫升催化剂接触。调节反应器温度以进行适当的转化。转化率表示为每一次通过乙苯的消失,且C8芳族化合物损失主要是变成苯和甲苯。结果如下:催化剂 A B温度,℃ 386 386乙苯转化率,% 28 27.5C8芳族化合物损失,% 2.8 2.7
Claims (7)
1.一种异构化二甲苯和乙苯的非平衡态进料混合物的方法,它包括使该进料混合物在氢气存在下在异构化区与一种包含有效量的SM-3结晶硅铝磷酸盐分子筛的催化剂复合体在可以得到一种包含比在该进料混合物中的比例高的对二甲苯的异构化产品的C8异构化条件下接触。
2.如权利要求1所述的方法,其特征在于该催化剂复合体包含有效量的铂族金属组分。
3.如权利要求1或2所述的方法,其特征在于该催化剂复合体还包括一种包括氧化铝和二氧化硅或其混合物的无机氧化物粘结剂。
4.如权利要求2所述的方法,其特征在于有效量的铂族金属组分以元素态计包含0.1-5%(质量)的铂。
5.如权利要求1或2所述的方法,其特征在于异构化产品包含大于平衡浓度的对二甲苯。
6.如权利要求1或2所述的方法,其特征在于该催化剂复合体包含以元素态计为0.1-5%(质量)的铂组分、10-100%(质量)的SM-3结晶硅铝磷酸盐分子筛和一种无机氧化物粘结剂。
7.如权利要求1或2所述的方法,其特征在于C8芳族化合物的异构化条件包括300-500℃的温度、101.3-5065kPa(1-50大气压)的压力、0.5-10hr-1的LHSV和0.5∶1-25∶1的氢/烃摩尔比。
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US5552182A (en) * | 1995-01-31 | 1996-09-03 | Rowland Institute For Science | Inking methods and compositions for production of digitized stereoscopic polarizing images |
-
1996
- 1996-04-12 ES ES96302578T patent/ES2140786T3/es not_active Expired - Lifetime
- 1996-04-12 PT PT96302578T patent/PT739873E/pt unknown
- 1996-04-12 AT AT96302578T patent/ATE188463T1/de not_active IP Right Cessation
- 1996-04-12 DE DE69605967T patent/DE69605967T2/de not_active Expired - Fee Related
- 1996-04-12 EP EP96302578A patent/EP0739873B1/en not_active Expired - Lifetime
- 1996-04-12 CA CA002174045A patent/CA2174045C/en not_active Expired - Fee Related
- 1996-04-12 DK DK96302578T patent/DK0739873T3/da active
- 1996-04-16 ZA ZA963008A patent/ZA963008B/xx unknown
- 1996-04-22 MX MX9601503A patent/MX9601503A/es not_active IP Right Cessation
- 1996-04-22 MY MYPI96001545A patent/MY121583A/en unknown
- 1996-04-22 AU AU50780/96A patent/AU702788B2/en not_active Ceased
- 1996-04-23 RO RO96-00853A patent/RO117968B1/ro unknown
- 1996-04-23 JP JP8100810A patent/JP2781544B2/ja not_active Expired - Fee Related
- 1996-04-23 KR KR1019960012353A patent/KR100197926B1/ko not_active IP Right Cessation
- 1996-04-23 RU RU96107973A patent/RU2125977C1/ru not_active IP Right Cessation
- 1996-04-23 SG SG1996009346A patent/SG43354A1/en unknown
- 1996-04-23 CN CN96105444A patent/CN1054596C/zh not_active Expired - Fee Related
- 1996-04-23 NO NO961613A patent/NO304936B1/no unknown
- 1996-06-04 TW TW085106655A patent/TW324713B/zh active
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1997
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2000
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1044615C (zh) * | 1997-03-26 | 1999-08-11 | 熊斌 | 一种代替乙炔气的液化烃类燃气 |
Also Published As
Publication number | Publication date |
---|---|
ES2140786T3 (es) | 2000-03-01 |
CA2174045C (en) | 2003-01-28 |
CN1054596C (zh) | 2000-07-19 |
EP0739873A1 (en) | 1996-10-30 |
DE69605967D1 (de) | 2000-02-10 |
JPH08310977A (ja) | 1996-11-26 |
ZA963008B (en) | 1996-11-27 |
SG43354A1 (en) | 1997-10-17 |
JP2781544B2 (ja) | 1998-07-30 |
KR960037626A (ko) | 1996-11-19 |
DK0739873T3 (da) | 2000-05-01 |
MY121583A (en) | 2006-02-28 |
TW324713B (en) | 1998-01-11 |
AU702788B2 (en) | 1999-03-04 |
DE69605967T2 (de) | 2000-10-05 |
ATE188463T1 (de) | 2000-01-15 |
NO304936B1 (no) | 1999-03-08 |
NO961613D0 (no) | 1996-04-23 |
AU5078096A (en) | 1996-11-07 |
RO117968B1 (ro) | 2002-11-29 |
EP0739873B1 (en) | 2000-01-05 |
KR100197926B1 (ko) | 1999-06-15 |
CA2174045A1 (en) | 1996-10-25 |
US5898090A (en) | 1999-04-27 |
MX9601503A (es) | 1997-04-30 |
NO961613L (no) | 1996-10-25 |
PT739873E (pt) | 2000-06-30 |
RU2125977C1 (ru) | 1999-02-10 |
GR3032969T3 (en) | 2000-07-31 |
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