CN112225630A - 煤基原料生产偏三甲苯的方法 - Google Patents
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Abstract
本发明涉及煤基原料生产偏三甲苯的方法。该方法以廉价的煤基粗苯和煤基粗甲醇为原料，采用外比表面积大(>90m2/g)、弱酸及中强酸为主(占总酸性位数量的95％以上)的烷基化催化剂和抗结焦烷基化反应介质(氢气与水或二氧化碳与水)，通过酸洗、加氢预处理、烷基化反应、精馏和物料循环的过程，高选择性(总包)的生产偏三甲苯。其中，烷基化反应在固定床、流化床或移动床反应器中进行，所使用的催化剂为两种金属氧化物助剂修饰的片状MCM‑56、纳米针状ZSM‑5、片状MCM‑49、纳米Beta分子筛，或其复合物。本发明所提供的方法能有效降低偏三甲苯的生产成本，并彻底实现其非石油路线生产。
Description
技术领域
本发明涉及一种以煤基原料生产偏三甲苯的方法。
背景技术
偏三甲苯作为一种重要的芳烃原料，可用作生产偏苯三酸酐和均三甲苯，并在溶剂行业有着广泛应用，需求量正逐年增加。目前，其生产完全依赖于石油资源，主要通过催化重整和石脑油裂解过程中产生的C9～C10芳烃馏分分离获得。我国矿藏是"多煤少油"，石油短缺将成为我国工业发展的主要瓶颈之一，国民经济的持续健康发展要求我国必须依托自身的资源优势来发展石化原料的生产技术，国家确立了"以煤代油"战略作为能源与资源的发展方向。同时，我国作为世界最大的煤焦炭产地，焦煤气与煤焦油是炼焦的主要副产，焦煤气经进一步分离从中可提取回收大量的粗苯，而煤焦油中重组分经加氢裂解轻质化，亦可得到粗苯(含甲苯)产品。随着近年煤化工行业的快速发展，我国焦化苯产能达400 万吨/年以上，产量约为300万吨/年，在苯总产量中的比率上升到近30％(其它为石油苯)，且大部分装置开工率严重不足。而且，焦化苯只能用于顺酐、医药、农药、合成橡胶、染料、溶剂等领域，其作为化工原料的应用范围与石油苯相比还较小，导致了焦化苯价格总是低于石油苯，所以焦化苯转化应用的新途径及其下游产品的开发引起了国内外的广泛关注。
以煤焦炉气、煤合成气为原料制甲醇技术已经非常成熟，随着近年来我国大量甲醇装置投产，甲醇产能严重过剩，价格持续走低。因此，针对国内煤转化与煤化工产业的特点，本发明提出一种以廉价的煤基粗苯与煤基粗甲醇为原料(无需分离提纯)，采用新型烷基化催化剂和抗结焦烷基化反应介质，通过一体化清洁转化，高选择性、低成本地生产偏三甲苯的方法，更有助偏三甲苯生成，可彻底实现偏三甲苯的非石油路线高效生产。
发明内容
本发明要解决的是当前偏三甲苯完全依赖石油路线生产的问题，提供了一种廉价煤基原料高选择性、低成本地生产偏三甲苯的方法。所述方法以煤基粗苯和煤基粗甲醇为原料，采用具有外比表面积大、弱酸和中强酸为主的新型烷基化催化剂和抗结焦的烷基化反应介质，通过酸洗、加氢预处理、烷基化反应、精馏和物料循环的过程，生产偏三甲苯。
煤基原料生产偏三甲苯的方法，以煤基粗苯和煤基粗甲醇为原料，采用外比表面积大、弱酸和中强酸为主的烷基化催化剂和抗结焦烷基化反应介质，通过酸洗、加氢预处理、烷基化反应、精馏和物料循环的过程，生产偏三甲苯。
作为本发明的优选，煤基粗甲醇原料中甲醇质量百分数含量为80.0％～ 93.0％，其他杂质组分包括水、二甲醚、乙醇、丁醇、戊醇；其中煤基粗甲醇为煤焦炉气所制粗甲醇、煤合成气所制粗甲醇中的至少一种。
作为本发明的优选，煤基粗苯为焦化粗苯、煤焦油重组分轻质化粗苯中的至少一种；煤基粗苯的成分中，除苯外，还含有质量百分数为0.5％～15.0％的甲苯和少量二甲苯及其他杂质(环己烷、含氮或含硫物质)。
作为本发明的优选，煤基粗苯经硫酸洗涤法酸洗后在固定床反应器中进行加氢预处理，与煤基甲醇进行烷基化反应；其中在加氢预处理时采用NiO-MoO3及 Co-MoO3催化剂。
作为本发明的优选，新型烷基化催化剂选自：两种金属氧化物助剂修饰的片状MCM-56、纳米针状ZSM-5、片状MCM-49或纳米Beta分子筛，或其两种复合物；其中两种金属氧化物助剂选自La2O3、CaO、Ce2O3、MgO和CuO，金属氧化物助剂总量的质量百分数为0.1％～10.0％。
作为本发明的优选，烷基化催化剂外比表面积大于90m2/g，外表面酸性位数量占总酸性位数量的30.0％以上，弱酸和中强酸数量占总酸性位数量的95％以上。
作为本发明的优选，抗结焦烷基化反应介质为氢气与水或二氧化碳与水。
作为本发明的优选，烷基化反应产物与未反应的苯进入精馏***，依次经过气提塔、苯+甲苯+二甲苯分离***，分离出的轻烃作为装置燃料，分离出的二甲苯循环作为反应原料；二甲苯分离***流出的重组分物料进入偏三甲苯精馏塔，分离得到高纯度偏三甲苯产品；偏三甲苯精馏塔流出的重组份物料作为装置液体燃料。
作为本发明的优选，烷基化反应器采用固定床反应器、流化床反应器和移动床反应器中的一种。
作为本发明的优选，烷基化反应条件为：烷基化反应条件为：煤基粗甲醇与煤基粗苯的摩尔比为1:1～1:6，反应压力为0.1MPa～5.0MPa，反应温度为350℃～700℃，抗结焦烷基化反应介质与原料摩尔比为1:2～10:1，总质量空速为0.2～10.0h-1；载气与原料摩尔比为1:2～10:1。
综上所述，本发明具有以下有益效果：
本发明中工艺***的总包入口物料为廉价的煤基粗苯与煤基粗甲醇，而产出高纯偏三甲苯产品，只副产少量的轻烃和少量重质芳烃，总包反应结果表现出很高的目标产物选择性；且省去了原料分离纯化工序，烷基化催化剂也无需频繁更换或再生循环，真正实现了非石油路线、高选择性、低成本地生产偏三甲苯。
附图说明
图1为本发明煤基原料生产偏三甲苯方法的工艺流程图。
具体实施方法
下面通过具体实施例对本发明进一步说明，但不局限于此。
实施例1:
图1所示为本发明中煤基原料生产偏三甲苯方法的工艺流程图。煤基原料生产偏三甲苯的方法，以煤合成气所制粗甲醇(80.0％)、焦化粗苯(含90.4wt％苯、8.0wt％甲苯、1.5wt％二甲苯和0.1wt％其他杂质)为原料，其中焦化粗苯经硫酸洗涤、加氢预处理(NiO-MoO3及Co-MoO3催化剂，固定床)后，与粗甲醇进入烷基化反应器(流化床)进行催化反应，得到产物主要为偏三甲苯、甲苯、混合二甲苯、少量重组份芳烃和轻烃。它们与未反应的苯进入精馏***，依次经气提塔、苯+甲苯+二甲苯(BTX)分离***，分离出的轻烃作为装置燃料，分离出的BTX循环作为反应原料；BTX分离***流出的重组分物料进入偏三甲苯精馏塔，分离得的高纯度偏三甲苯产品；偏三甲苯精馏塔流出的重组份物料作为装置液体燃料。烷基化反应所用催化剂为2.0％La2O3和1.8％Ce2O3复合修饰的纳米针状ZSM-5分子筛，外比表面积为96m2/g，外表面酸性位数量占总酸性位数量的 34％，弱酸和中强酸性位数量占总酸性位数量的96.8％。烷基化反应条件为：甲醇与芳烃(BTX)摩尔比为1:6，反应压力为常压，反应温度为350℃，水与原料摩尔比为1:2，总质量空速为4.0h-1；采用CO2为反应载气，载气与原料摩尔比为3:1。即以廉价的煤合成气粗甲醇和焦化粗苯为原料，通过上述工艺方法，实现高选择性、低成本地生产偏三甲苯。整套工艺***总包反应数据如下：苯和甲醇完全转化，芳烃产物中偏三甲苯的选择性达到94.0％。烷基化催化剂单程运行寿命达820h(当烷基化反应器中甲醇不能完全转化时，认为催化剂失活，以下实施例相同)。其中，芳烃产物中偏三甲苯选择性的计算方法如下(以下实施例相同)：
实施例2:
基于实施例1，与实施例1不同之处在于：
煤基甲醇原料采用煤焦炉气所制粗甲醇(甲醇含量93.0wt％)。煤基苯采用焦化粗苯和煤焦油重组分轻质化粗苯的混合物，含79.8wt％苯、15.0wt％甲苯、 5.0wt％二甲苯和0.2wt％其他杂质。烷基化反应器采用固定床反应器。烷基化反应所用催化剂为0.04％CuO和0.1％CaO复合修饰的片状MCM-56/纳米Beta复合分子筛，外比表面积为93m2/g，外表面酸性位数量占总酸性位数量的32％，弱酸和中强酸性位数量占总酸性位数量的98.1％。烷基化反应条件为：甲醇与芳烃(BTX) 的摩尔比为1:1，反应压力为2.0MPa，反应温度为480℃，水与原料摩尔比为4:1，总质量空速为10.0h-1；采用H2为反应载气，载气与原料摩尔比为10:1。其他工艺安排和原料选择与实施例1相同。本实施例中整套工艺***总包反应数据如下：苯和甲醇完全转化，芳烃产物中偏三甲苯的选择性达到95.4％。烷基化催化剂单程寿命达2500h。
实施例3:
基于实施例1，与实施例1不同之处在于：
煤基苯原料采用焦化粗苯，含99.19wt％苯、0.6wt％甲苯、0.2wt％二甲苯和0.01wt％其他杂质；煤基甲醇采用煤合成气所制粗甲苯与煤焦炉气所制粗甲醇的混合物，含84.1wt％的甲醇；烷基化反应器采用移动床反应器。烷基化反应所用催化剂为5.0％CdO和5.0％MgO复合修饰的纳米针状ZSM-5/片状MCM-49复合分子筛，外比表面积为99m2/g，外表面酸性位数量占总酸性位数量的36％，弱酸和中强酸性位数量占总酸性位数量的97.1％。烷基化反应条件为：甲醇与芳烃(BTX) 的摩尔比为1:2，反应压力为5.0MPa，反应温度为700℃，水与原料摩尔比为 10:1，总质量空速为0.2h-1；采用CO2为反应载气，载气与原料摩尔比为1:2。其他原料选择和工艺安排与实施例1相同。整套工艺体系总包反应数据如下：苯和甲醇完全转化，芳烃产物中偏三甲苯选择性达到96.6％。烷基化催化剂单程寿命达1600h。
实施例4:
基于实施例1，与实施例1不同之处在于：
煤基甲醇原料采用煤合成气所制粗甲醇和焦炉气所制粗甲醇的混合物(甲醇含量86.3wt％)；煤基苯采用煤焦油重组分轻质化粗苯(含79.0wt％苯、15.0wt％甲苯、5.0wt％二甲苯和1.0wt％其他杂质)；烷基化反应所用催化剂为3.0％CuO 和1.0％MgO修饰的片状MCM-49/纳米Beta复合分子筛，外比表面积为92m2/g，外表面酸性位数量占总酸性位数量的35％，弱酸和中强酸性位数量占总酸性位数量的95.7％。其他原料选择、工艺安排、反应条件与实施例2相同。整套工艺***总包反应数据如下：苯和甲醇完全转化，芳烃产物中偏三甲苯的选择性达到96.3％。烷基化催化剂单程寿命达2700h。
上面所述的实施例仅是对本发明的优选实施方式进行描述，并非对本发明的构思和范围进行限定。在不脱离本发明设计构思的前提下，本领域普通人员对本发明的技术方案做出的各种变型和改进，均应落入到本发明的保护范围，本发明请求保护的技术内容，已经全部记载在权利要求书中。
Claims (10)
1.煤基原料生产偏三甲苯的方法，其特征在于，以煤基粗苯和煤基粗甲醇为原料，采用外比表面积大、弱酸和中强酸为主的烷基化催化剂和抗结焦烷基化反应介质，通过酸洗、加氢预处理、烷基化反应、精馏和物料循环的过程，生产偏三甲苯。
2.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，煤基粗甲醇原料中甲醇质量百分数含量为80.0％～93.0％，其他杂质组分包括水、二甲醚、乙醇、丁醇、戊醇；其中煤基粗甲醇为煤焦炉气所制粗甲醇、煤合成气所制粗甲醇中的至少一种。
3.根据权利要求1或2所述的煤基原料生产偏三甲苯的方法，其特征在于，煤基粗苯为焦化粗苯、煤焦油重组分轻质化粗苯中的至少一种；煤基粗苯的成分中，除苯外，还含有质量百分数为0.5％～15.0％的甲苯和少量二甲苯及其他杂质(环己烷、含氮或含硫物质)。
4.根据权利要求3所述的煤基原料生产偏三甲苯的方法，其特征在于，煤基粗苯经硫酸洗涤法酸洗后在固定床反应器中进行加氢预处理，与煤基甲醇进行烷基化反应；其中在加氢预处理时采用NiO-MoO3及Co-MoO3催化剂。
5.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，新型烷基化催化剂选自：两种金属氧化物助剂修饰的片状MCM-56、纳米针状ZSM-5、片状MCM-49或纳米Beta分子筛，或其两种复合物；其中两种金属氧化物助剂选自La2O3、CaO、Ce2O3、MgO和CuO，金属氧化物助剂总量的质量百分数为0.1％～10.0％。
6.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，烷基化催化剂外比表面积大于90m2/g，外表面酸性位数量占总酸性位数量的30.0％以上，弱酸和中强酸数量占总酸性位数量的95％以上。
7.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，抗结焦烷基化反应介质为氢气与水或二氧化碳与水。
8.根据权利要求1所述的煤基原料生产偏三甲苯方法，其特征在于，烷基化反应产物与未反应的苯进入精馏***，依次经过气提塔、苯+甲苯+二甲苯分离***，分离出的轻烃作为装置燃料，分离出的二甲苯循环作为反应原料；二甲苯分离***流出的重组分物料进入偏三甲苯精馏塔，分离得到高纯度偏三甲苯产品；偏三甲苯精馏塔流出的重组份物料作为装置液体燃料。
9.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，烷基化反应器采用固定床反应器、流化床反应器和移动床反应器中的一种。
10.根据权利要求1所述的煤基原料生产偏三甲苯的方法，其特征在于，烷基化反应条件为：煤基粗甲醇与煤基粗苯的摩尔比为1:1～1:6，反应压力为0.1MPa～5.0MPa，反应温度为350℃～700℃，抗结焦烷基化反应介质与原料摩尔比为1:2～10:1，总质量空速为0.2～10.0h-1；载气与原料摩尔比为1:2～10:1。
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| CN107473918A (zh) * | 2017-07-14 | 2017-12-15 | 同济大学 | 煤基原料生产对二甲苯、邻二甲苯和偏三甲苯的方法 |
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| GB1210786A (en) * | 1968-04-18 | 1970-10-28 | Mobil Oil Corp | Hydrocarbon conversion employing highly selective catalysts |
| CN101654394A (zh) * | 2009-09-11 | 2010-02-24 | 上海卓悦化工科技有限公司 | 一种btx芳烃甲基化合成偏三甲苯的方法 |
| CN107473918A (zh) * | 2017-07-14 | 2017-12-15 | 同济大学 | 煤基原料生产对二甲苯、邻二甲苯和偏三甲苯的方法 |
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