CN101048229A - 重质芳烃转化催化剂组合物及相关方法 - Google Patents

重质芳烃转化催化剂组合物及相关方法 Download PDF

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CN101048229A
CN101048229A CNA2005800372959A CN200580037295A CN101048229A CN 101048229 A CN101048229 A CN 101048229A CN A2005800372959 A CNA2005800372959 A CN A2005800372959A CN 200580037295 A CN200580037295 A CN 200580037295A CN 101048229 A CN101048229 A CN 101048229A
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carbon monoxide
olefin polymeric
catalyst
benzene
molecular sieve
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T·麦克明
D·A·施塔赫尔奇克
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Abstract

本发明公开了催化剂组合物，制备该组合物的方法和用于转化含有C9+芳烃的原料以形成含有更轻质芳烃产物并且含有低于大约0.5wt％乙基苯的得到产物的方法，其中wt％以所得产物的C8芳烃级分的重量为基准计。C9+芳烃在烷基转移反应条件下转化为含有二甲苯的反应产物。该催化剂组合物包括(i)具有至少300的α值的酸性组分；和(ii)具有至少300的氢化活性的氢化组分。该组合物可以通过将至少一种氢化组分引入到具有至少300的α值的酸性组分中来制备。

Description

重质芳烃转化催化剂组合物及相关方法
领域
本发明涉及可用于将重质芳烃，尤其C9+芳烃，转化为更轻质的芳烃产物，尤其苯、甲苯和二甲苯(下文统称为BTX)的催化剂组合物，生产该组合物的方法和在重质芳烃转化方法中使用该组合物的方法。
背景
苯和二甲苯的来源是催化重整产物，它通过让石脑油和氢的混合物与在适中酸性载体例如卤素处理的氧化铝上的强氢化/脱氢催化剂例如铂接触来制备。通常，从该重整产物中分离出C6-C8级分，用对芳族化合物或脂族化合物具有选择性的溶剂萃取，以获得相对不含脂族化合物的芳族化合物的混合物。该芳族化合物的混合物通常含有BTX及乙基苯。
炼油厂也已集中精力于通过C9+芳族化合物和甲苯用含贵金属的沸石催化剂烷基转移来生产苯和二甲苯。在C9+芳族化合物和甲苯用含贵金属的催化剂的烷基转移中，形成了高价值石化产品例如苯和二甲苯、还有乙基苯。对所得转化产物进一步分离非芳族化合物、苯、C8芳族化合物(即，乙基苯，对二甲苯，间二甲苯和邻二甲苯)、未反应的甲苯以及未反应的C9+芳族化合物。通常，对C8芳族产物进行进一步分离，以获得二甲苯，尤其对二甲苯。降低C8芳族化合物中的乙基苯的量改进了二甲苯回收的效率。因此，存在着强大的经济和技术动力来降低烷基转移产物中的乙基苯浓度。烷基转移产物中的乙基苯的量主要取决于(a)原料组成以及(b)烷基转移催化剂和烷基转移条件。通常，C9+芳烃原料和/或甲苯进料含有基于该原料总重量的0.001-4wt％的乙基苯杂质。除了原料中的乙基苯以外，乙基苯可以在烷基转移过程中由含有乙基的C9+芳烃和由各种副反应形成。
在重质芳烃的烷基转移过程中解决烷基转移产物中的乙基苯问题的一个办法公开于US专利No.5,942,651中，包括让含有C9+芳烃和甲苯的进料在烷基转移反应条件下与第一催化剂组合物和氢化组分接触的步骤，该第一催化剂组合物含有约束指数为0.5-3的沸石例如ZSM-12。从该第一接触步骤获得的流出物然后与第二催化剂组合物接触，以产生包括苯和二甲苯的烷基转移反应产物，该第二催化剂组合物含有约束指数为3-12的沸石例如ZSM-5，并且该第二催化剂组合物可在与第一催化剂组合物不同的床或反应器中。进料中的乙基苯和/或在烷基转移过程中形成的乙基苯部分被乙基苯脱烷基为苯和乙烯的反应所破坏。
US专利No.5,905,051公开了通过让烃料流例如C9+芳族化合物与含有第一催化剂组合物和第二催化剂组合物的催化剂体系接触而将该料流转化为C6-C8芳烃例如二甲苯的方法，其中所述催化剂组合物存在于不同阶段，并且不进行物理混合或共混，其中所述第一催化剂组合物是金属促进的氧化铝或硅石结合的β沸石，所述第二催化剂组合物是引入了选自硅、磷、硫和它们的组合中的活性促进剂的ZSM-5。根据’051专利，使用不同的催化阶段改进了C9+芳族化合物和萘类至二甲苯的转化，并且降低了产物中的不希望有的乙基苯的量。’051产物中的乙基苯是大约3-7wt％乙基苯，以所得产物中C8芳烃级分的重量为基准计。
现已发现，包括分子筛的催化剂体系表现了增强的酸性和充分脱除C9+芳烃进料中的含乙基的芳族化合物的氢化活性，而C9+进料转化为有用化合物例如二甲苯的转化率没有总体降低。
概述
在一个实施方案中，本发明涉及催化剂组合物，包括：
i)具有至少300的α值的酸性组分；和
ii)具有至少300的氢化活性的氢化组分。
在另一个实施方案中，本发明涉及制备催化剂组合物的方法，包括：
i)让具有至少300的α值的酸性组分与至少一种氢化组分在足以将所述氢化组分引入到所述酸性组分中的条件下接触，以形成改性的酸性组分；和
ii)将所述改性的酸性组分煅烧，以产生所述具有至少300的氢化活性的催化剂。
在另一个实施方案中，本发明涉及转化含有C9+芳烃的原料以形成含有更轻质芳烃产物和低于大约0.5wt％乙基苯的得到产物的方法，所述wt％以所得产物的C8芳烃级分的重量为基准计，所述方法包括让所述原料在烷基转移反应条件下与催化剂组合物接触，该催化剂组合物包括：i)具有至少300的α值的酸性组分；和ii)具有至少300的氢化活性的氢化组分，所述C9+芳烃在所述烷基转移反应条件下转化为含有二甲苯的反应产物。优选地，以所得产物的C8芳烃级分的重量为基准计，该芳烃产物含有低于大约0.3wt％的乙基苯。更优选地，以所得产物的C8芳烃级分的重量为基准计，该芳烃产物含有低于大约0.2wt％的乙基苯。
优选地，所述酸性组分包括第一分子筛，该第一分子筛选自具有MTW结构的分子筛，具有MOR结构的分子筛，以及X射线衍射图含有在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的d-间距最大值()的多孔结晶无机氧化物材料。更优选地，所述催化剂包括分子筛ZSM-12。可供选择地，所述多孔结晶无机氧化物材料选自MCM-22、PSH-3、SSZ-25、MCM-36、MCM-49和MCM-56中的一种或多种。
在另一个实施方案中，所述催化剂包括约束指数为3-12的第二分子筛。优选地，该第二分子筛是ZSM-5。优选地，所述催化剂包括两种分子筛，第一分子筛是ZSM-12和第二分子筛是ZSM-5。适宜地，所述催化剂组合物为颗粒状物，以及第一和第二分子筛各自被包含于相同的催化剂颗粒中。
优选地，所述氢化组分选自VIIIB族和VIIB族金属中的一种或多种。更优选地，所述氢化组分选自铼、铂和钯中的一种或多种。
通常，所述进料含有苯或甲苯。在另一个方面，本发明涉及制备苯的方法，该方法包括以下步骤：(a)让C9+芳烃和甲苯在烷基转移反应条件下在催化剂组合物上反应，该催化剂组合物包括(i)具有至少300的α值的酸性组分；和(ii)具有至少300的氢化活性的氢化组分，以形成含有苯和二甲苯类的得到产物流；和(b)从所述产物流中蒸馏出苯，获得苯产物。优选地，该芳烃产物含有低于大约0.5wt％的乙基苯，以所得产物的C8芳烃级分的重量为基准计。更优选地，该芳烃产物含有低于大约0.3wt％的乙基苯，以所得产物的C8芳烃级分的重量为基准计。更优选地，该芳烃产物含有低于大约0.2wt％的乙基苯，以所得产物的C8芳烃级分的重量为基准计。
在又一个方面，本发明涉及至少以10千克/小时的速率处理C9+芳烃的方法。
实施方案的详细描述
在一个优选实施方案中，本发明提供了一种催化剂组合物，包括：
(i)具有至少300的α值、优选至少400的α值、更优选至少500的α值的酸性组分；和(ii)具有至少300的氢化活性、优选至少500的氢化活性、更优选至少1000的氢化活性的氢化组分。
优选地，所述酸性组分包括第一分子筛，该第一分子筛选自具有MTW结构的分子筛，具有MOR结构的分子筛，以及X射线衍射图含有在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的d-间距最大值()的多孔结晶无机氧化物材料中的一种或多种。更优选地，所述催化剂包括分子筛ZSM-12。可供选择地，所述该多孔结晶无机氧化物材料选自MCM-22、PSH-3、SSZ-25、MCM-36、MCM-49和MCM-56。
在另一个实施方案中，所述催化剂包括约束指数为3-12的第二分子筛。优选地，第二分子筛是ZSM-5。优选地，所述催化剂包括两种分子筛，第一分子筛是ZSM-12和第二分子筛是ZSM-5。适宜地，所述催化剂组合物为颗粒状物，以及第一和第二分子筛各自被包含于相同的催化剂颗粒中。
优选地，所述氢化组分选自VIIIB族和VIIB族金属中的一种或多种。更优选地，所述氢化组分选自铼、铂和钯中的一种或多种。
在另一个实施方案中，本发明涉及制备催化剂组合物的方法，包括：
i)让具有至少300的α值的酸性组分与至少一种氢化组分在足以将所述氢化组分引入到所述酸性组分中的条件下接触，以形成改性的酸性组分；和
ii)将所述改性的酸性组分煅烧，以产生所述具有至少300的氢化活性的催化剂。
优选地，所述氢化组分通过离子交换、始润浸渍法、固态反应或它们的两种或多种的组合而引入到所述酸性组分中。更优选地，所述氢化组分通过离子交换和/或始润浸渍法引入到所述酸性组分中。
在另一个实施方案中，本发明涉及转化含有C9+芳烃的原料以形成含有更轻质芳烃产物和低于大约0.5wt％乙基苯的得到产物的方法，所述wt％以所得产物的C8芳烃级分的重量为基准计，所述方法包括让所述原料在烷基转移反应条件下与催化剂组合物接触，所述催化剂组合物包括：(i)具有至少300的α值的酸性组分；和(ii)具有至少300的氢化活性的氢化组分，C9+芳烃在所述烷基转移反应条件下转化为含有二甲苯的反应产物。优选地，以所得产物的C8芳烃级分的重量为基准计，该芳烃产物含有低于大约0.3wt％的乙基苯。更优选地，以所得产物的C8芳烃级分的重量为基准计，该芳烃产物含有低于大约0.2wt％的乙基苯。
本文所使用的术语“更轻质芳烃产物”被定义为指产物中的芳烃分子，其碳原子数少于原料中的芳烃分子的碳原子数。例如，对二甲苯是C9+与甲苯和/或苯的烷基转移产物之一，具有8个碳原子，少于C9+芳烃分子中的9个或更多个碳原子。
催化剂组合物
在本发明的方法中使用的催化剂组合物包括：
(i)具有至少300的α值的酸性组分；和
(ii)具有至少300的氢化活性的氢化组分。
所述酸性组分是具有至少300的α值的材料，例如硅石-氧化铝；酸性氧化锆；选自具有MTW结构的分子筛，具有MOR结构的分子筛和X射线衍射图含有在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的d-间距最大值()的多孔结晶无机氧化物材料中的分子筛。
关于分子筛，ZSM-12更具体地在US专利No.3,832,449中有描述。丝光沸石天然存在，但还可以使用其合成形式之一例如TEA-丝光沸石(即，由包括四乙基铵导向剂的反应混合物制备的合成丝光沸石)，这在US专利Nos.3,766,093和3,894,104中被公开。具有规定X射线衍射图的适合的多孔结晶无机氧化物材料的实例包括MCM-22、PSH-3、SSZ-25、MCM-36、MCM-49和MCM-56。MCM-22在US专利No.4,954,325中有描述，PSH-3在US专利No.4,439,409中有描述，SSZ-25在US专利No.4,826,667中有描述，MCM-36在US专利No.5,250,277中有描述，MCM-49在US专利No.5,236,575中有描述，以及MCM-56在US专利No.5,362,697中有描述。上述每一篇专利的全部内容引入本文供参考。
关于分子筛，适合的具有约束指数为3-12的材料包括ZSM-5，ZSM-11，ZSM-22，ZSM-23，ZSM-35，ZSM-48，ZSM-57和ZSM-58。ZSM-5在US专利No.3,702,886中有描述。ZSM-11在US专利No.3,709,979中有描述。ZSM-22在US专利No.5,336,478中有描述。ZSM-23在US专利No.4,076,842中有描述。ZSM-35在US专利No.4,016,245中有描述。ZSM-48在US专利No.4,375,573中有描述。ZSM-57在US专利No.4,873,067中有描述。ZSM-58在US专利No.4,698,217中有描述。约束指数及其测定方法在US专利No.4,016,218中有描述。上述每一篇专利的全部内容引入本文供参考。
通常，基于所述催化剂组合物中第一和第二分子筛的总重量，第二分子筛为0-95wt％，例如超过20至80wt％。
在第一分子筛为ZSM-12的情况下，ZSM-12可以具有包括以下摩尔关系的组成：
                    X2O3：(n)YO2
其中X是三价元素，例如铝、硼、铁、铟和/或镓，优选铝；Y是四价元素，例如硅、锡和/或锗，优选硅；和n小于75，例如20到小于60。可以进一步选择ZSM-12，以便具有小于0.1微米，例如大约0.05微米的平均晶体粒度；以及至少1000×10-6sec-1，例如至少2000×10-6sec-1的1，3，5-三甲苯扩散参数D/r2，当在100℃的温度和2托的1，3，5-三甲苯压力下测定时。
本文所使用的特定多孔结晶材料的扩散参数被定义为D/r2×106，其中D是扩散系数(cm2/sec)，r是晶体半径(cm)。所需的扩散参数可以由吸附测量法得出，前提是假设平片(plane sheet)模型描述了该扩散过程。因此，对于既定吸附物载量Q，值Q/Q∞(其中Q∞是平衡吸附物载量)与(Dt2/r)1/2数学相关，其中t是达到吸附物载量Q所需的时间(sec)。用于平片模型的图解法由J.Crank在“The Mathematics ofDiffusion”(牛津大学出版社，Ely House，伦敦，1967)中给出。
用作第一分子筛的ZSM-12还可以被设计成具有至少150，例如至少300的α值。α值测试是催化剂的裂化活性的衡量标准，并且在US专利No.3,354,078和 Journal of Catalysis，第4卷，第527页(1965)；第6卷，第278页(1966)；和第61卷，第395页(1980)中有描述，这些文献各自关于该方面的描述引入本文供参考。这里所使用的测试实验条件包括538℃的恒定温度和不变的流速，如在 Journal of Catalysis，第61卷，第395页中详细说明的。
在前一段落中所述的具有组成、晶体粒度、扩散参数和α值的ZSM-12可以通过含有碱金属或碱土金属(M)阳离子(通常钠)源，三价元素(X)的氧化物(通常氧化铝)，四价元素(Y)的氧化物(通常硅石)，甲基三乙基铵离子(R)(通常作为碘盐存在)，羟基离子和水的合成混合物结晶来制备。该合成混合物可以具有如下所示的按氧化物的摩尔比计的组成：
    组分     有效     优选
    YO2/X2O3     20-100     40-80
    H2O/YO2     10-100     15-40
    OH-/YO2     0.1-0.6     0.15-0.4
    R/YO2     0.1-0.6     0.15-0.4
    M/YO2     0.1-0.6     0.15-0.4
所述合成混合物还可以含有ZSM-12的成核种子，在存在这种种子的情况下，它们一般占该混合物的0.05-5wt％。该合成混合物可以在搅拌或静止条件下，优选在搅拌条件下，在≤160℃，例如140-160℃的温度下结晶48-500小时，此后，从母液中分离出所得ZSM-12晶体，并回收。
可能理想的是，在所述催化剂组合物中引入每一种分子筛与耐受在本发明的烷基转移方法中所使用的温度和其它条件的另一材料。此类材料包括活性和无活性材料与合成或天然存在的沸石，以及无机材料，例如粘土、硅石和/或金属氧化物，比如氧化铝。该无机材料可以是天然存在的形式，或凝胶状沉淀物或凝胶的形式，包括硅石和金属氧化物的混合物。
本身具有催化活性的材料与每一种分子筛联合使用(即，与之结合或在其合成过程中存在)可以改变所述催化剂组合物的转化率和/或选择性。无活性材料适合用作稀释剂，以控制转化的量，使得烷基转移产物能够以经济和有序方式获得，无需使用控制反应速率的其它方式。这些催化活性或无活性材料可以例如引入到天然存在的粘土(如膨润土和高岭土)中，以改进所述催化剂组合物在工业操作条件下的压碎强度。提供具有良好压碎强度的催化剂组合物是理想的，因为在工业应用中，希望防止催化剂组合物破碎成粉末状材料。
可以作为所述催化剂组合物的粘结剂与分子筛复合的天然存在的粘土包括蒙脱石和高岭土家族，该家族包括变膨润土和通常被称为迪西粘土(Dixie)、麦克纳米粘土(McNamee)、乔治亚粘土(Georgiaclay)和佛罗里达白土(Florida clay)等的那些高岭土，其中主要矿物成分是埃洛石(haloysite)、高岭石、地开石、珍珠陶土或蠕陶土。这些粘土可以按初始开采的原状态使用，或者首先进行煅烧、酸处理或化学改性。
除了上述材料以外，所述分子筛可以与多孔基质粘结剂材料例如无机氧化物复合，该无机氧化物选自硅石、氧化铝、氧化锆、二氧化钛、氧化钍、氧化铍、氧化镁和它们组合，例如硅石-氧化铝、硅石-氧化镁、硅石-氧化锆、硅石-氧化钍、硅石-氧化铍、硅石-二氧化钛以及三元组合物，例如硅石-氧化铝-氧化钍、硅石-氧化铝-氧化锆、硅石-氧化铝-氧化镁和硅石-氧化镁-氧化锆。还可以有利地提供至少部分为胶体状态的以上多孔基质粘结剂材料，以有利于所述催化剂组合物的挤出。
每一种分子筛通常与所述粘结剂或基质材料混合，使得最终催化剂组合物含有5-90wt％，通常10-60wt％的粘结剂或基质材料。
在本发明的方法中，第一和第二分子筛被包含于同一催化剂床中。通常，这通过物理混合各种分子筛的不同颗粒(优选以结合形式)或通过共挤出分子筛混合物(通常与粘结剂)来实现，使得最终催化剂组合物的每一颗粒含有第一和第二分子筛。可供选择地，第一和第二分子筛之一的颗粒可以作为所述第一和第二分子筛的另一种的粘结剂形成，如在国际专利公开No.WO97/45198中所述；该专利的全部内容引入本文供参考。
在所述催化剂组合物中，至少第一分子筛(优选每一种分子筛)具有与之相关的至少一种氢化组分，例如钨，钒，钼，铼，铬，锰，选自元素周期表(CAS版，1979)IB、IIB、IIIB、IVB、VB、VIB、VIIB和VIIIB族中的金属，或它们的混合物。有用的VIIIB族金属包括铁，钌，锇，镍，钴，铑，铱，以及贵金属例如铂、铼或钯。优选地，氢化组分是钯、铂或铼。
氢化组分的量根据氢化活性和催化功能之间的平衡来选择。当使用相对于钯的活性最高的金属例如铂时(钯不具有这种强氢化活性)，需要较少的氢化组分。一般，所述催化剂组合物含有低于10wt％的氢化组分，通常0.01-2wt％的所述组分。
所述氢化组分可以通过共结晶引入到催化剂组合物中，交换到组合物中以达到IIIA族元素例如铝在分子筛结构中的程度，在其中浸渍，或与分子筛和粘结剂混合。这种组分可以被浸渍于分子筛内或分子筛上，例如，在铂的情况下，通过用含有含铂金属的离子的溶液处理分子筛。适合于用于用铂浸渍催化剂的铂化合物包括氯铂酸、氯化亚铂和各种含有铂胺配合物的化合物，例如Pt(NH3)4Cl2·H2O。
可供选择地，所述氢化组分的化合物可以在分子筛与粘结剂复合时或在分子筛和粘结剂已通过挤出或造粒形成为颗粒之后加入到分子筛中。
所述氢化组分还可以设计成具有至少300、例如至少500、优选至少1000的氢化值的氢化活性。氢化功能通过比较烷基转移产物中的乙烯的量与乙烷的量来测定。通过乙基取代的芳烃分子的脱烷基以及脂族和环烷族烃的裂化，在烷基转移方法中形成了乙烯。氢化组分被设计成在这些乙烯分子能够参与副反应之前使它们饱和成乙烷。氢化组分越好，在烷基转移产物中相对于乙烷的乙烯量越少。氢化值被定义为乙烷与乙烯的比率。本文所使用的测试实验条件包括412℃的恒定温度，2170kPAa的压力，2的氢与烃摩尔比，2的甲苯/1，4-甲基乙基苯比率和2.7h-1的WHSV。用乙烷/乙烯比率衡量的氢化值通过产物中的乙烷的摩尔百分率除以产物中乙烯的摩尔百分率来计算。
在用氢化组分处理后，所述分子筛通常通过在65-160℃，一般110-143℃的温度和100-200kPAa的压力下加热至少1分钟和通常不长于24小时来干燥。此后，所述分子筛可以在干燥气流，例如空气流或氮气流中在260-650℃的温度下煅烧1-20小时。煅烧一般在100-300kPAa的压力和大约0.002到大约20h-1的WHSV下进行。
使用前，可以对所述催化剂组合物采用蒸汽处理来将该催化剂组合物的芳烃氢化活性减至最小。在蒸汽处理过程中，催化剂组合物通常与5-100％蒸汽在至少260-650℃的温度和100-2590kPAa的压力以及大约0.002到大约20h-1的WHSV下接触至少1小时，尤其1-20小时。
另外，在将所述催化剂组合物与烃进料接触之前，可以对所述氢化组分进行硫化。这适宜地通过让催化剂与硫源例如硫化氢在大约320-480℃的温度下接触来完成。该硫源可以经由载气例如氢气或氮气与催化剂接触。
在将所述催化剂组合物与烃进料接触之后，由于焦化或金属附聚，该催化剂可能被钝化。该钝化催化剂可以适当地通过用含有氧或含氧化合物比如臭氧、氯氧化物(oxochlorine)、二氧化碳等的料流燃烧焦炭，使用氧化还原循环、氯氧化物处理等再分散金属，用液体烃或无机和/或有机化合物例如水、乙醇、丙酮等洗涤，或用包括氢的料流恢复活性来再生。再生或恢复活性可以在环境温度到大约600℃的温度范围，大约100到大约5000kPAa的压力范围和大约0.2到大约100h-1的WHSV下进行。
进料
在本发明的方法中使用的芳烃进料包括乙基苯和一种或多种含有至少9个碳原子的芳族化合物。存在于典型进料中的具体C9+芳族化合物包括均三甲苯(1，3，5-三甲苯)，均四甲苯(1，2，4，5-四甲苯)，连三甲苯(1，2，3-三甲苯)，假枯烯(1，2，4-三甲苯)，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，丁基取代的苯和二甲基乙基苯类。适合的C9+芳烃源是富含芳烃的来源于任何炼油工艺的任何C9+级分。该芳烃级分含有大量的C9+芳烃，例如至少80wt％C9+芳烃，其中优选至少80wt％和更优选超过90wt％的烃类为C9-C12。可以有用的典型炼油级分包括催化重整产物、FCC石脑油或TCC石脑油。
所述进料还可以包括苯或甲苯。因此，在一个实际实施方案中，烷基转移反应器的进料包括乙基苯、C9+芳烃和甲苯。该进料还可以包括通过蒸馏烷基转移反应本身的流出产物所获得的再循环/未反应/生成的苯、甲苯、乙基苯和C9+芳烃。通常，甲苯占大约5到大约90wt％，C9+占大约10到大约95wt％。在典型轻质进料中，甲苯占整个进料的大约40到大约90wt％，例如50-70wt％，而C9+芳烃组分占烷基转移反应区的整个进料的10-60wt％，例如30-50wt％。在典型重质进料中，甲苯占整个进料的大约15到大约50wt％，例如25-40wt％，而C9+芳烃组分占烷基转移反应区的整个进料的50-85wt％，例如60-75wt％。
烃转化方法
所述方法可以在任何适当的反应器内进行，包括径向流、固定床、连续流或流化床反应器。烷基转移反应条件一般包括大约343到大约510℃，例如大约400到大约454℃的温度；大约380到大约4240kPAa，例如大约1480到大约3550kPAa的压力；大约1到大约5，例如大约1到大约3的氢与烃摩尔比；和大约0.2到大约20h-1，例如大约1到大约5h-1的WHSV。烷基转移反应条件足以将重质芳烃进料转化为含有大量的C6-C8芳烃化合物，例如苯、甲苯和二甲苯，尤其苯和二甲苯的产物。烷基转移反应条件还足以将进料中的乙基苯转化为苯和乙烷。
现在通过参考下列实施例来详细说明本发明。
实施例1  催化剂制备
由包括11280g的水、1210g的甲基三乙基氯化铵(MTEAC1)、1950g的购自Degussa的Ultrasil PM、229g的铝酸钠溶液(45％)和364g的50％氢氧化钠溶液的混合物合成小晶体、高活性ZSM-12。该混合物具有以下摩尔组成：
SiO2/Al2O3＝50
H2O/SiO2＝22
OH-/SiO2＝0.2
Na+/SiO2＝0.2
MTEACl/SiO2＝0.26
让所述混合物在160℃下在5加仑高压釜内于150RPM下搅拌的同时反应144小时。将产物过滤，用去离子(DI)水洗涤和在120℃下干燥。接合成原样的(as-synthesized)材料的XRD图显示了典型纯相的ZSM-12拓扑结构。接合成原样的材料的SEM显示，该材料由小晶体(具有大约0.05微米的平均晶体尺寸)的附聚物组成。
通过在室温下用硝酸铵溶液进行两次离子交换，随后在120℃下干燥和在540℃下煅烧6小时，将所述按合成原样的晶体转化为氢化形式。所得ZSM-12晶体具有4 4.98的SiO2/Al2O3摩尔比，500的α值以及在100℃的温度和2托的均三甲苯压力下高于5000×10-6sec-1的对于均三甲苯的D/r2。
将含有65wt％的以上生产的ZSM-12、15wt％ZSM-5和20wt％氧化铝的混合物挤出为长度1.3mm并具有方形(quadrulobe)横断面的粒料。该粒料在120℃下干燥，然后在氮气中在480℃下煅烧3小时。该材料然后与硝酸铵交换，在120℃下干燥，然后在空气中在540℃下煅烧6小时。然后通过始润浸渍法由四胺硝酸铼的水溶液将0.5wt％Re加入到催化剂中。将该浸渍材料在120℃下干燥，然后在空气中在350℃下煅烧，形成最终催化剂。
实施例2
使用3g由实施例1得到的催化剂组合物，在大约412℃的温度，2170kPAa的压力，2的氢与烃摩尔比和2.7h-1的WHSV下使具有表1中给出的组成的甲苯/C9+芳烃混合物进行烷基转移反应。以下表1总结了投入生产4.4天后的结果。
                    表1
wt％，H/C基准     进料     产物
C5-     8.55
非芳烃     0.17     0.16
苯     12.87
甲苯     61.27     38.01
乙基苯     0.03     0.06
二甲苯     0.26     30.37
C9     29.73     8.76
C10     8.25     0.87
C11+     0.30     1.09
总计     100     100
A9转化率(％)     71
A10转化率(％)     89
脱乙基率(％)     98
二甲苯收率(％)     30
C8芳烃中的乙基苯(％)     0.19
乙烷/乙烯     4000
二甲苯/乙基苯比率     506
表1中的结果显示，实施例1的催化剂具有高活性，尤其就乙基苯的脱乙基率来说(98％的脱乙基率和506的二甲苯/乙基苯比率)。表1中的结果还显示，实施例1的催化剂具有C9+至二甲苯的高转化活性。
实施例3
使用3g由实施例1得到的催化剂组合物，在大约412℃的温度，2170kPAa的压力，2的氢与烃摩尔比和2.7h-1的WHSV下使具有表2中给出的组成的甲苯/C9+芳烃混合物进行烷基转移反应。以下表2总结了投入生产4.4天后的结果。
                        表2
wt％，H/C基准     进料     产物
C5-     14.31
非芳烃     0.14     0.02
苯     6.09
甲苯     14.77     25.20
乙基苯     0.01     0.07
二甲苯     0.75     33.26
C9     67.77     17.90
C10     16.29     2.86
C11+     0.28     1.24
总计     100     100
A9转化率(％)     74
A10转化率(％)     89
脱乙基率(％)     98
二甲苯收率(％)     33
C8芳烃中的乙基苯(％)     0.20
乙烷/乙烯     13411
二甲苯/乙基苯比率     475
表2中的结果显示，实施例1的催化剂具有高活性，尤其就乙基苯的脱乙基率来说(98％的脱乙基率和475的二甲苯/乙基苯比率)。表2中的结果还显示，实施例1的催化剂具有C9+至二甲苯的高转化活性。
所有专利、专利申请、试验程序、优先权文件、文章、出版物、手册和这里引用的其它文件以此类公开与本发明一致的程度和这种引入被允许的全部权限全面引入供参考。
当本文列举数值下限和数值上限时，从任何下限到任何上限的范围被考虑在内。
虽然特别地描述了本发明的示例性实施方案，但应该理解的是，不偏离本发明的精神和范围的各种其它变型是本领域技术人员所显而易见并且可以容易做出的。因此，所附权利要求书的范围不限于本文所给出的实施例和描述，反而，该权利要求书被视为囊括了存在于本发明中的所有具有专利新颖性的特征，包括本发明所属领域技术人员作为同等物处理的所有特征。

Claims (19)

1、催化剂组合物，包括：
i)具有至少300的α值的酸性组分；和
ii)具有至少300的氢化活性的氢化组分。
2、如权利要求1所述的催化剂组合物，其中所述酸性组分具有至少1000的α值。
3、如前述权利要求的任何一项所述的催化剂组合物，其中所述氢化组分具有至少1000的氢化活性。
4、如前述权利要求的任何一项所述的催化剂组合物，其中所述酸性组分和所述氢化组分形成了结合了该两种组分的单独颗粒。
5、如前述权利要求的任何一项所述的催化剂组合物，其中所述酸性组分包括第一分子筛；该第一分子筛选自具有MTW结构的分子筛，具有MOR结构的分子筛，以及X射线衍射图含有在12.4±0.25，6.9±0.15，3.57±0.07和3.42±0.07处的d-间距最大值()的多孔结晶无机氧化物材料中的一种或多种。
6、如权利要求5所述的催化剂组合物，其中所述多孔结晶无机氧化物材料选自MCM-22、P8H-3、SSZ-25、MCM-36、MCM-49和MCM-56。
7、如权利要求5-6的任何一项所述的催化剂组合物，其中所述催化剂进一步包括约束指数为3-12的第二分子筛。
8、如权利要求5-7的任何一项所述的催化剂组合物，其中所述第一分子筛是ZSM-12。
9、如权利要求7所述的催化剂组合物，其中所述第二分子筛是ZSM-5。
10、如前述权利要求的任何一项所述的催化剂组合物，其中所述氢化组分选自VIIIB族和VIIB族金属中的一种或多种。
11、如权利要求10所述的催化剂组合物，其中所述氢化组分选自铼、铂和钯中的一种或多种。
12、制备前述权利要求的任何一项所述的催化剂组合物的方法，所述方法包括以下步骤：
i)让酸性组分与至少一种氢化组分在足以将所述氢化组分引入到所述酸性组分中的条件下接触，以形成改性的酸性组分；和
ii)将所述改性的酸性组分煅烧，以产生所述催化剂。
13、如权利要求12所述的方法，其中所述接触步骤选自离子交换、始润浸渍法、所述氢化组分与所述酸性组分和/或粘结剂的机械混合、以及它们的组合。
14、如权利要求12-13的任何一项所述的方法，其中所述煅烧条件包括大约260到大约650℃的温度、大约100到大约300kPa-a的压力和大约0.002到大约20h-1的WHSV。
15、转化含有C9+芳烃的原料以形成C9+芳烃含量少于所述原料中的C9+芳烃并且含有低于大约0.5wt％乙基苯的得到产物的方法，所述wt％以所得产物的C8芳烃级分的重量为基准计，所述方法包括让所述原料在烷基转移反应条件下与权利要求1-11的任何一项所述的催化剂组合物接触。
16、如权利要求15所述的方法，其中基于所述原料的重量，所述乙基苯以大约0.001到大约4wt％的量存在于所述原料中。
17、如权利要求15-16的任何一项所述的方法，其中所述烷基转移反应条件包括大约343到大约510℃的温度；大约380到大约4240kPa-a的压力；大约1到大约5的氢与烃摩尔比；和大约0.2到大约20h-1的WHSV。
18、如权利要求15-17的任何一项所述的方法，进一步包括催化剂再生和/或催化剂活性恢复步骤，其中所述催化剂再生和/或催化剂活性恢复包括以下步骤：
i)让所述催化剂与含氧料流在再生所述催化剂的条件下接触，或
ii)让所述催化剂与含氢料流在恢复所述催化剂的活性的条件下接触。
19、制备苯的方法，该方法包括以下步骤：
(a)让C9+芳烃和甲苯在烷基转移反应条件下在权利要求1-11的任何一项所述的催化剂组合物上反应，以形成含有苯和二甲苯类的得到产物流；和
(b)从所述产物流中蒸馏出苯，获得苯产物。
CNA2005800372959A 2004-11-05 2005-09-16 重质芳烃转化催化剂组合物及相关方法 Pending CN101048229A (zh)

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