CN114073964A - 一种钯合金催化剂氢解木质素到芳烃的方法 - Google Patents

一种钯合金催化剂氢解木质素到芳烃的方法 Download PDF

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CN114073964A
CN114073964A CN202010814119.8A CN202010814119A CN114073964A CN 114073964 A CN114073964 A CN 114073964A CN 202010814119 A CN202010814119 A CN 202010814119A CN 114073964 A CN114073964 A CN 114073964A
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alloy catalyst
aromatic hydrocarbon
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张波
李昌志
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种钯合金催化剂氢解木质素到芳烃的方法，以钯合金为催化剂，以烷烃为反应溶剂，充入H2，底物在压力为0.5‑3MPa，温度为80‑300℃下反应2‑12h。使用该方法催化氢解木质素模型化合物或木质素原材料到芳烃的转化率最高可达99％，产物收率最高可达99％。本发明的原料木质素是自然界中最丰富的天然可再生芳香化合物资源，来源广泛，成本低廉，不消耗化石资源，符合可持续发展要求。

Description

一种钯合金催化剂氢解木质素到芳烃的方法
技术领域
本发明涉及生物质资源利用技术领域，具体涉及一种钯合金催化剂氢解木质素制备芳烃的方法。
背景技术
芳烃是有机化学工业最基本的原料之一，苯、甲苯、二甲苯的产量和规模仅次于乙烯和丙烯。目前，芳烃主要来源于石油和煤焦油的催化重整技术，随着化石能源日益消耗及带来的环境污染和气候变化等问题，发展可再生资源制备芳烃化学品不仅可以解决能源危机而且可以促进社会可持续发展，具有双重意义。
木质素是自然界最大量的可再生芳香环资源，木质素主要含有对羟苯基丙烷、愈创木基丙烷和紫丁香基丙烷三种结构单元，对应的前驱体分别是香豆醇、松柏醇和芥子醇。木质素是这些单体通过脱氢聚合，由碳碳键和碳氧键等连接无序组合，具有化学性质顽固，难以解聚的特点。现阶段，每年造纸行业产生的制浆废液中约含有5000万吨的木质素，大部分的木质素以废液的形式排入江河或直接烧掉，不仅造成资源浪费，同时又污染环境。因此，开发一条不依赖石油资源制备芳烃及其衍生物的可再生技术路线显得尤为重要。
目前，木质素降解利用途径主要有热裂解，催化氧化和催化氢解三种。热裂解通常需要较高温度，存在能耗高的问题，且裂解后的生物油热值较低，通常需要进一步提质才能作为运输燃料使用。催化氢解与催化氧化是选择切断木质素芳醚键获取芳香化合物的两种主要策略。从木质素制备芳烃的关键步骤是催化剂断裂C-O键的同时脱掉甲氧基和羟基，并且使苯环未被破环，这是一大难点与挑战。因此，发展利用高选择性地加氢脱氧木质素到芳烃的催化剂是解决以上问题的关键。
发明内容
基于以上问题，本发明提供一种钯合金催化剂Pd-M，通过该催化剂中的Pd-M两种金属之间的相互作用，以及该催化剂的可调控性，实现氢解木质素制备芳烃化合物，为木质素高选择转化制备芳香化合物提供绿色高效的新途径。
本发明的技术方案如下：
一种钯合金催化剂氢解木质素到芳烃的方法，以烷烃为反应溶剂，充入H2，在钯合金催化剂的作用下，底物在压力为0.5～3MPa，温度为80～300℃下反应2～12h制备芳烃；底物为木质素模型化合物或木质素原材料。
进一步地，钯合金催化剂为Pd-M/ZrO2；金属M负载量为1wt％～5wt％，Pd负载量为1wt％～5wt％。
进一步地，金属M是Ru、Co、Ni、Cu、Zn、Fe、Mn、Ag、W、Re、Mo、Nb、V中的一种。
进一步地，底物溶于溶剂，底物的质量浓度为0.05～0.5mg/mL，钯合金催化剂与底物的质量比为0.01～0.1。
进一步地，木质素模型化合物为苯酚、愈创木酚、2-甲氧基-4-甲基苯酚、2-甲氧基-4-乙基苯酚、2-甲氧基-4-丙基苯酚、2,6-二甲氧基苯酚、2,6-二甲氧基-4-甲基苯酚、2,6-二甲氧基-4-乙基苯酚、2,6-二甲氧基-4-丙基苯酚、2-(2-甲氧基苯氧基)-1-苯基乙醇、苯基苄基醚或二苯醚中的一种或多种。
进一步地，木质素原材料为有机木质素、木质素磺酸钙、碱木质素、磨木木质素或酶解木质素中的一种或多种。
进一步地，芳烃为苯、甲苯、乙苯、丙苯、邻二甲苯、间二甲苯或对二甲苯中的一种或多种。
进一步地，烷烃为正己烷、环己烷、环戊烷、正十二烷或正十三烷中的一种或多种。
与现有技术相比，本发明具有如下优点：
1.催化剂中M与Pd为双活性组分，两者协同催化，同时金属负载量低，原子利用率高，产物选择性最高可达99％。
2.与现有两步法制备芳烃相比，本发明一步实现了从木质素原材料到芳烃的技术路线。
3.反应过程中不使用无机酸、碱，避免了木质素降解工艺中催化大量碱液的产生，避免了常见的环境污染问题，反应过程环境友好。
4.与现有石油基工业合成路线制备芳烃相比，本发明的原料木质素是自然界中最丰富的天然可再生芳香化合物资源，来源广泛，成本低廉，不消耗化石资源，具有原料可再生的优点，符合可持续发展的要求。
具体实施方式
实施例中所述木质素原材料中有机木质素是依据文献提取(Green Chem.2019,21,803–811)；磨木木质素是依据文献提取(纤维素科学与技术，2018,26,9-18)，酶解木质素来源于山东龙力生物科技股份有限公司，其余木质素原材料都是购买获得(木质素磺酸钙：CAS 8061-52-7和碱木质素：CAS 9005-53-2，购买于上海麦克林生化科技有限公司)。
所述木质素模型化合物2-(2-甲氧基苯氧基)-1-苯基乙醇是依据文献(J.Am.Chem.Soc.2010,132,12554)中合成，其余木质素单体如苯酚(CAS 108-95-2)，愈创木酚(CAS 90-05-1)，2-甲氧基-4-甲基苯酚(CAS 93-51-6)，2-甲氧基-4-乙基苯酚(CAS2785-89-9)，2,6-二甲氧基苯酚(CAS 91-10-1)，苯基苄基醚(CAS 946-80-5)购买于上海麦克林生化科技有限公司；2,6-二甲氧基-4-丙基苯酚(CAS 6766-82-1)购买于上海源叶生物科技有限公司。
实施例1-11
Pd-M合金催化剂的制备：
(1)将35mgM前驱体，25mg四氯钯酸钠和1gZrO2超声溶于10mL去离子水中，搅拌浸渍6h；
(2)配制10mmol的碳酸钠溶液，并用该溶液加入(1)反应液调节pH值至8后，过滤；
(3)将(2)过滤后的固体加入10mL 0.1M的NaBH4，搅拌2h；
(4)将(3)溶液过滤后的固体放入60℃烘箱内干燥12h后，转移到120℃烘箱内干燥12h；
(5)将(4)得到的固体放置在焙烧炉中，在氢气气氛中500℃焙烧3h，升温速率为2℃/min，完成后钝化并降至室温，制备出Pd-M/ZrO2催化剂。
表1催化剂组分
Figure BDA0002632056960000031
Figure BDA0002632056960000041
注：各实施例中M负载量为1wt％，Pd的负载量为1wt％。
实施例12-26
将100mg苯酚和10mgPdCu合金催化剂(1wt％Cu,1wt％Pd)置于反应釜中，加入20mL环戊烷溶剂，用氢气置换六次后置于一定压力状态，将反应釜密闭并升温至适当温度，以550转/min的速度进行搅拌反应一定时间。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，产物定性分析通过GC-MS联用技术及标样对照，定量分析通过气相色谱内标法实现。
表2.PdCu合金催化剂催化苯酚制备苯的性能测试
Figure BDA0002632056960000042
实施例27
将100mg愈创木酚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于1.5MPa H2，将反应釜密闭并升温至250℃，以550转/min的速度进行搅拌反应一定时间。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为96.3％，苯收率为90.2％。
实施例28
将100mg 2-甲氧基-4-甲基苯酚和10mg PdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于1.5MPa H2，将反应釜密闭并升温至250℃，以550转/min的速度进行搅拌反应8h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为95.3％，甲苯收率为91.2％。
实施例29
将100mg 2-甲氧基-4-乙基苯酚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于1.5MPa H2，将反应釜密闭并升温至250℃，以550转/min的速度进行搅拌反应8h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为96.8％，乙苯收率为90.9％。
实施例30
将100mg 2-甲氧基-4-丙基苯酚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于1.5MPa H2，将反应釜密闭并升温至250℃，以550转/min的速度进行搅拌反应8h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为94.2％，丙苯收率为87.8％。
实施例31
将100mg 2,6-二甲氧基苯酚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于3MPa H2，将反应釜密闭并升温至300℃，以550转/min的速度进行搅拌反应10h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为97.2％，苯收率为94.5％。
实施例32
将100mg 2,6-二甲氧基-4-丙基苯酚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于3MPa H2，将反应釜密闭并升温至300℃，以550转/min的速度进行搅拌10h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为93.2％，丙苯收率为85.2％。
实施例33
将100mg 2-(2-甲氧基苯氧基)-1-苯基乙醇和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于3MPa H2，将反应釜密闭并升温至300℃，以550转/min的速度进行搅拌12h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为89.2％，苯收率为83.2％，乙苯收率为79.4％。
实施例34
将100mg苯基苄基醚和10mgPdCu合金催化剂置于反应釜中，加入20mL环己烷溶剂，用氢气置换六次后置于3MPa H2，将反应釜密闭并升温至300℃，以550转/min的速度进行搅拌10h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，转化率为94.8％，苯收率为88.6％，甲苯收率为78.3％。
实施例35-43
将100mg苯酚和钯合金催化剂置于反应釜中，加入20mL环戊烷溶剂，用氢气置换六次后置于1.5MPa H2，将反应釜密闭并升温至250℃，以550转/min的速度进行搅拌反应10h。反应结束后，降至室温，取1.5mL反应液用滤头过滤于色谱小瓶中，产物定性分析通过GC-MS联用技术及标样对照，定量分析通过气相色谱内标法实现。
表3.Pd-M合金催化剂催化氢解苯酚到苯
Figure BDA0002632056960000061
Figure BDA0002632056960000071
实施例44-48
将100mg木质素原材料和200mgPd-Fe合金催化剂置于反应釜中，加入50mL环戊烷溶剂，用氢气置换六次后置于3MPa H2，将反应釜密闭并升温至300℃，以550转/min的速度进行搅拌反应12h。反应结束后，降至室温，将反应液过滤至圆底烧瓶中旋蒸，加入2mL含内标的甲醇溶液，取1.5mL该溶液于色谱小瓶中，产物定性分析通过GC-MS联用技术及标样对照，定量分析通过气相色谱内标法实现。
表4.合金催化剂Pd-Fe催化解聚真实木质素的反应结果
Figure BDA0002632056960000072
对比例1
利用Ru/Nb2O5为催化剂催化转化有机桦木木质素，以H2O为反应溶剂，在250℃,0.7MPa H2条件下反应20h，得到20.4wt％的芳烃收率，8.6wt％的环烷烃收率。
对比例2
利用W2C/MCM-41为催化剂，在750℃温度下20秒快速热裂解碱木质素，获得芳烃的选择性为85％。
对比例3
通过两步法催化转化木质素为芳烃的方法，首先，在氢气压力2.0-10MPa条件下，在极性溶剂中，在加氢解聚催化剂作用下加氢解聚反应，反应温度为250-500℃，反应时间为2-24h，木质素氢解得到酚类油混合物；而后旋蒸步骤得到的酚类油混合物，在氢气压力10MPa条件下，在溶剂中，Ru/HZSM-5作用下加氢脱氧反应，反应温度为200℃，反应时间3h，得到芳烃收率为71.5％。

Claims (8)

1.一种钯合金催化剂氢解木质素到芳烃的方法，其特征在于，所述方法以烷烃为反应溶剂，充入H2，在钯合金催化剂的作用下，底物在压力为0.5-3MPa，温度为80-300℃下反应2-12h制备芳烃；所述底物为木质素模型化合物或木质素原材料。
2.根据权利要求1所述的方法，其特征在于，所述钯合金催化剂为Pd-M/ZrO2；金属M负载量为1wt％～5wt％，Pd负载量为1wt％～5wt％。
3.根据权利要求2所述的方法，其特征在于，所述金属M是Ru、Co、Ni、Cu、Zn、Fe、Mn、Ag、W、Re、Mo、Nb、V中的一种。
4.根据权利要求1所述的方法，其特征在于，所述底物的质量浓度为0.05～0.5mg/mL，钯合金催化剂与底物的质量比为0.01～0.1。
5.根据权利要求1所述的方法，其特征在于，所述木质素模型化合物为苯酚、愈创木酚、2-甲氧基-4-甲基苯酚、2-甲氧基-4-乙基苯酚、2-甲氧基-4-丙基苯酚、2,6-二甲氧基苯酚、2,6-二甲氧基-4-甲基苯酚、2,6-二甲氧基-4-乙基苯酚、2,6-二甲氧基-4-丙基苯酚、2-(2-甲氧基苯氧基)-1-苯基乙醇、苯基苄基醚或二苯醚中的一种或多种。
6.根据权利要求1所述的方法，其特征在于，所述木质素原材料为有机木质素、木质素磺酸钙、碱木质素、磨木木质素或酶解木质素中的一种或多种。
7.根据权利要求1所述的方法，其特征在于，所述芳烃为苯、甲苯、乙苯、丙苯、邻二甲苯、间二甲苯或对二甲苯中的一种或多种。
8.根据权利要求1所述的方法，其特征在于，所述烷烃为正己烷、环己烷、环戊烷、正十二烷或正十三烷中的一种或多种。
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