CN111423303A - 一种低温芳构化方法 - Google Patents
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Abstract
本发明属于石油化工技术领域，具体涉及一种低温芳构化方法。本发明是使用布朗斯特酸‑路易斯酸双酸离子液体作为催化剂，含有叔碳原子的环烷烃为产品分布调节剂。在氮气或氢气氛围下，对轻烃进行芳构化反应，得到芳构化产物。本发明利用离子液体低温高活性的特点，首次将含有叔碳原子的环烷烃作为芳构化产物调节剂应用到轻烃芳构化反应中，这对低温芳构化技术发展具有十分重要的意义及使用价值。
Description
技术领域
本发明属于石油化工领域，具体涉及一种低温芳构化方法。
背景技术
芳烃通常是指苯（Benzene，简称B）、甲苯（Toluene，简称T）、和二甲苯（Xylene，简称X）是重要的基础化工原料，同时也是调节汽油辛烷值的常用调和组分。近年来，我国芳烃的需求量迅猛增长，产能产量的发展却严重滞后，因此提芳烃的产能产量，研发芳烃化新技术已刻不容缓。轻烃芳构化技术通常是指小分子烃类在催化剂的作用下经过脱氢、裂解、齐聚、氢转移、环化及异构化等复合反应步骤制备芳烃的技术。该技术的关键是催化剂的研发和催化工艺过程开发。
现有文献、专利中，用于轻烃芳构化技术的催化剂普遍为分子筛等固体催化剂，且反应温度都比较高。如英国石油公司(BP)与美国UOP开发的负载型Pt/Al2O3、Pd/Al2O3催化剂，在反应温度高于为550℃的情况下，烷烃转化为芳烃，该反应伴随着严重裂解副反应，同时Pt、Pd为贵金属，成本较高(Csicsery S. Dehydrocyclodimerization of butanes oversupported platimun[J]. Journal of Catalysis, 1970, 17:207-215)。美国Mobile公司以HZSM-5为催化剂，虽将芳构化反应温度降为425℃，但仍反应过程仍然出现了严重的积碳(Chen N, Yan Y. M2-forming- A process for aromatization of light hydrocarbons[J]. Industrial & Engineering Chemistry Process Design and Development, 1986,25: 151-155)。万海等（万海. 新型L沸石基轻烃芳构化催化剂的制备及反应研究[D].2015.）以分级制备的Ga1.0-ZSM-5/Pt0.6-L复合分子筛为催化剂，芳构化选择性提高的同时反应温度却高达500℃。以上所述这些工业催化剂大多需要在较高的温度和氢气氛围下操作且易出现活性组分流失、积碳以及能耗和成本双高的缺点。因此，开发低温、低耗的芳构化催化剂是解决芳构化技术瓶颈的关键。
离子液体因其众多增强性能而具有广泛而又前景的应用。目前具有路易斯酸酸性的离子液体催化剂普遍用于烷烃烷基化反应(Cui, P, Zhao G, Ren H, et al. Ionicliquid enhanced alkylation of iso-butane and 1-butene [J]. Catalysis Today,2013, 200: 30-35)和异构化反应(Zhang R, Meng X, Liu Z, et al. Isomerization ofn-pentane catalyzed by acidic chloroaluminate ionic liquids[J]. Industrial &Engineering Chemistry Research, 2008, 47: 8205-8210)中。本发明首次开发以布朗斯特酸-路易斯酸双酸离子液体为催化剂，含有叔碳原子的环烷烃为产品分布调节剂的轻烃芳构化技术，对芳构化技术发展具有十分重要的意义及使用价值。此外，本发明方法制备工艺简单，操作简便，成本低廉，具备良好的经济效益和工业化潜力。
发明内容
为解决上述技术问题，本发明的目的在于设计一种低温芳构化方法。将布朗斯特酸-路易斯酸双酸离子液体作为催化剂、含有叔碳原子的环烷烃作为产品分布调节剂与轻烃原料置于反应釜内，在气氛氛围下，低温反应得到芳烃。
为了实现上述目的，本发明采用如下技术方案：
一种低温芳构化方法，具体包括以下步骤：
（1）布朗斯特酸-路易斯酸双酸离子液体催化剂的合成：本发明中所采用的离子液体均可采用本领域技术人员知悉的公知现有技术方法制备。
（2）低温芳构化过程：称取上述离子液体催化剂、含有叔碳原子的环烷烃与轻烃到高压反应釜中混合均匀，离子液体催化剂与轻烃质量比为0.01-10，轻烃与叔碳原子的环烷烃质量比为0.01-0.1。在气氛氛围下，低温反应得到芳烃。
其中，原料轻烃为C1-C8的烷烃或烯烃，叔碳原子环烷烃产品分布调节剂为甲基环己烷、甲基环戊烷、(邻、间、对)二甲基环己烷、2, 2, 6-三甲基环庚烷的单环或双环烷烃类中的任意一种。
其中，所述布朗斯特酸-路易斯酸双酸离子液体为咪唑、吡啶、季铵型或季膦型离子液体中的任意一种，分别是以下列具体结构式表示的化合物：
式中，X-为AlCl4 -, Al2Cl7 -, CuAlCl5 -, AlBr4 -中的一种或多种；R为C1-C8的直链烷基中的任意一种；R`为无、C1-C8直链烷基中的任意一种、COOH、-PO4H2或-SO3H酸根；n=1-6。
进一步地，反应压力为0-1 MPa，反应温度为0-120℃，催化反应时间为0.5-60 h，所述气体氛围为氮气、氢气中的一种或两种。
本发明的优点在于：
本发明提供的上述轻烃芳构化方法，相对现有的分子筛类催化剂，在低温下以叔碳原子环烷烃为产品调节剂高产率合成芳烃产品。具有以下优点：
（1）离子液体催化剂具有良好溶解性、低挥发性、热稳性高、液态存在温度范围宽、可设计性和可重复性等优点；
（2）实验过程操作压力、温度都大大降低，克服了现有分子筛催化剂芳构化工艺反应温度较高的苛刻条件，降低了能耗，降低了该技术应用的综合成本，含叔碳原子环烷烃产品分布调节剂的加入明显提高了芳烃产率，具备良好的经济效益和工业化潜力。
附图说明
图1 正己烷在离子液体上芳构化的推测反应机理。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，以下的实施例将对本发明进行更为全面的描述，但不能理解为对本发明可实施范围的限定。
以下实施例中采用的离子液体催化剂均按照常规方法合成得到。
实施例1
以质量比0.2:1（以正己烷10 g为基准）的离子液体催化剂A ([HO3SC3NEt3]Cl -5AlCl3)（制备方法参照Industrial & Engineering Chemistry Research, 2008, 47:8205-8210）与正己烷加入高压釜内，通入氮气，控制初压为0.1 MPa，搅拌速度为500 rpm，反应温度控制在20℃，反应3 h，得到芳烃总含量为0.888，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
正己烷在离子液体上芳构化的推测反应机理如下图1：
首先正己烷在L酸酸位上形成碳正离子中间体，然后在B酸上形成烯烃中间体、二聚物中间体，直至环化中间体，最后在L酸位上脱氢生成芳烃，在此过程中含叔碳原子环烷烃的加入稳定碳正离子且诱导环烷烃中间体的产生，从而提高芳烃的产率。
实施例2
以质量比0.1:0.02:1（以正己烷10 g为基准）的离子液体催化剂A ([HO3SC3NEt3]Cl -5AlCl3)、甲基环己烷与正己烷加入高压釜内，通入氮气，控制初压为0.1 MPa，搅拌速度为500 rpm，反应温度控制在20℃，反应3 h，得到芳烃总含量为0.888，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例3
以质量比0.1:0.05:1（以正己烷10 g为基准）的离子液体催化剂A ([HO3SC3NEt3]Cl -5AlCl3)、甲基环己烷与正己烷加入高压釜内，通入氮气，控制初压为0.5 MPa，搅拌速度为500 rpm，反应温度控制在30℃，反应3 h，得到芳烃总含量为1.256，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例4
以质量比0.1:0.1:1（以正己烷10 g为基准）的离子液体催化剂B ([HO3SC3NEt3]Br -5AlBr3)（该化合物为自制化合物）、甲基环戊烷与正己烷加入高压釜内，通入氮气，控制初压为0.5 MPa，搅拌速度为500 rpm，反应温度控制在30℃，反应3 h，得到芳烃总含量为1.256，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例5
以质量比1:2（以正己烷10 g为基准）的离子液体催化剂C ([HO3SC3NEt3]Cl -5AlCl3-0.67CuCl)，以甲基环戊烷与正己烷（二者质量比为0.01-0.1）加入高压釜内，通入氮气，控制初压为1 MPa，搅拌速度为500 rpm，反应温度控制在40℃，反应3 h，得到芳烃总含量为1.619，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例6
以质量比0.2:0.1:2（以正己烷10 g为基准）的离子液体催化剂C ([HO3SC3NEt3]Cl -5AlCl3-0.67CuCl)、对二甲基环己烷与正己烷加入高压釜内，通入氮气，控制初压为1 MPa，搅拌速度为500 rpm，反应温度控制在40℃，反应3 h，得到芳烃总含量为1.619，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例7
以质量比1:1（以正戊烯10 g为基准）的离子液体催化剂A ([HO3SC3NEt3]Cl -5AlCl3)与正戊烯加入高压釜内，通入氮气，再放气关阀，控制初压为室压，搅拌速度为500 rpm，反应温度控制在100℃，反应3 h，得到芳烃总含量为3.990，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
实施例8
以质量比0.01:0.1:1（以正戊烯10 g为基准）的离子液体催化剂A ([HO3SC3NEt3]Cl -5AlCl3)、甲基环己烷与正戊烯加入高压釜内，通入氮气，再放气关阀，控制初压为室压，搅拌速度为500 rpm，反应温度控制在100℃，反应3 h，得到芳烃总含量为6.698，所得芳烃包括苯、甲苯和二甲苯，具体数据见表1。
对比例1
本对比例采用一种未经修饰的ZSM-5分子筛作为催化剂，以便与实施例1进行对比。
以质量比1:3（以正己烷10 g为基准）的ZSM-5分子筛催化剂与正己烷加入高压釜内，通入氮气，控制初压为1 MPa，搅拌速度为500 rpm，反应温度控制在20℃，反应3 h。
对比例2
本对比例采用一种未经修饰的ZSM-5分子筛作为催化剂，以便与实施例1进行对比。
以质量比1:3（以正己烷10 g为基准）的ZSM-5分子筛催化剂与正己烷加入高压釜内，通入氮气，控制初压为1 MPa，搅拌速度为500 rpm，反应温度控制在50℃，反应3 h。
对比例3
本对比例采用一种未经修饰的ZSM-5分子筛作为催化剂，以便与实施例1进行对比。
以质量比1:3（以正己烷10 g为基准）的ZSM-5分子筛催化剂与正己烷加入高压釜内，通入氮气，控制初压为1 MPa，搅拌速度为500 rpm，反应温度控制在100℃，反应24 h。
表1 轻烃芳构化结果一览表
从表1的数据可以看出，本发明所述的离子液体催化剂具有明显的芳构化反应活性，因此具备轻质烃类芳构化反应的能力。并且与对比例相比，传统的分子筛催化剂在低温条件下轻质烃类芳构化催化反应活性。因此，本发明所述的离子液体催化剂具有低温催化轻质烃类转化成芳烃的能力，具有操作简便，成本低廉，具备良好的经济效益和工业化潜力。
显然，上述实施例仅为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或变动。这里也无法对所有的实施方式予以穷举。而非所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (9)
1.一种低温芳构化方法，其特征在于：以布朗斯特酸-路易斯酸双酸离子液体为催化剂，含有叔碳原子的环烷烃作为产品分布调节剂，在气体氛围下，将离子液体、含有叔碳原子的环烷烃以及轻烃原料置于反应釜内混合均匀并反应得到芳烃。
2.根据权利要求1所述的低温芳构化方法，其特征在于：所述布朗斯特酸-路易斯酸双酸离子液体为咪唑、吡啶、季铵型或季膦型双酸离子液体中的任意一种，分别是以下列具体结构式表示的化合物：
式中，X-为AlCl4 -, Al2Cl6Br-, GaCl4 -, Al2Cl7 -, CuAlCl5 -, AlBr4 -中的一种或多种；R为C1-C8的直链烷基中的任意一种；R`为无、C1-C8直链烷基中的任意一种、-COOH、-PO4H2或-SO3H酸根；n=1-6。
3.根据权利要求1所述的低温芳构化方法，其特征在于：所述含叔碳原子环烷烃产品分布调节剂为甲基环己烷、甲基环戊烷、(邻、间、对)二甲基环己烷、2, 2, 6-三甲基环庚烷的单环或双环烷烃类中的任意一种。
4.根据权利要求1所述的低温芳构化方法，其特征在于：所述轻烃原料为C1-C8的烷烃或烯烃。
5.根据权利要求1所述的低温芳构化方法，其特征在于：所述叔碳原子环烷烃类产品分布调节剂与轻烃原料的质量比为0.01-0.1。
6.根据权利要求1所述的低温芳构化方法，其特征在于：所述离子液体与轻烃原料的质量比为0.01-10。
7.根据权利要求1所述的低温芳构化方法，其特征在于：所述反应温度为0-120℃，反应压力为0-1 MPa。
8.根据权利要求1所述的低温芳构化方法，其特征在于：所述气体氛围为氮气、氢气中的一种或两种。
9.根据权利要求1所述的低温芳构化方法，其特征在于：所述反应时间为0.5-60 h。
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