CN109647441B - 一种单原子催化剂在木质素催化加氢制芳香化合物中的应用 - Google Patents
一种单原子催化剂在木质素催化加氢制芳香化合物中的应用 Download PDFInfo
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Abstract
本发明涉及木质素加氢选择解聚，具体地说是一种单原子催化剂在木质素催化加氢制芳香化合物中的应用；该方法以多种β‑O‑4模型分子和有机木质素、木质素磺酸盐、碱木质素为原料，在150℃‑240℃，0.7‑3.0MPa的氢气氛中实现高选择性裂解芳醚键获得芳香族化合物。β‑O‑4模型分子转化率最高达99％，愈创木酚产率最高达93％，苯乙烯收率最高达65％；以不同木质素为原料转化时，芳香族生物油收率为38‑70％。本发明使用可再生天然生物质为原料，原料廉价且来源广泛；反应过程无需使用无机酸、碱，避免了传统木质素催化大量碱液的产生；具有反应条件温和、活性和选择性高、反应过程环境友好等特征。
Description
技术领域
本发明涉及木质素解聚制备芳香族化合物，具体地说是一种单原子催化剂 M1/MoS2催化剂(M＝Fe,Ni,Ru,Rh,Pd,Pt,Ir)催化木质素资源裂解制备芳香族化合物的方法。
背景技术
生物质具有环境友好和可再生等性质，可以实现CO2的零排放，是全球最大的唯一可以转变为液态烃类的能源材料。以生物质为原料制备液体燃料和化学品，对于解决化石资源短缺和地区分配不均、减轻环境污染、实现经济可持续发展具有重大意义。
木质素是作为生物质资源重要组成部分，占植物干重的15-30％，是自然界中唯一可以提供芳香化学品的可再生碳资源。目前，造纸行业中每年产生的木质素，只有不到2％的被用于工业生产，其余大部分都被任意排入河流或者直接燃烧，这不仅造成了资源的浪费，同时也给环境带了重大的压力，由此产生的废水占到全国工业废水量的30％，是我国工业废水控制的第一对象。
芳香族化合物在化学工业中有极为重要的应用，例如苯酚和对苯二甲酸及其衍生物不仅是应用广泛的大宗化学品，同时也是生产树脂、橡胶、医药中间体及其它精细化学品的重要原料。从结构上看，木质素是以芳环为结构主体的三维网状聚合物，结构单元之间通过醚键或碳碳键相连。选择性切断木质素结构单元之间的链接可实现由木质素资源制备芳香族化合物，从而作为化石资源的替代品获得应用，在一定程度上减轻世界能源危机的窘境，同时也避免了废弃“黑液”的排放。
目前木质素的选择解聚主要包括酸碱解聚、催化氢化、氧化解聚、高温热解及生物催化解聚等几种方法(Chemical Reviews,2015,15, 11559-11624)。其中选择催化氢解是不破坏芳环情况下选择切断木质素芳醚键获得酚类化合物的一种解聚策略，是木质素利用的关键途径之一。催化氢解反应中，贵金属催化剂由于具有较强的加氢活性，被大量用于木质素氢解反应研究中。北京大学寇元教授课题组较早用Pd/C，Pt/C，Ru/C等作催化剂，以磷酸为助剂，氢解白桦木质素获得单酚类产率46.4％。Lercher 课题组最近对贵金属催化木质素及模型化合物的涉氢反应机理进行了大量研究，发现该过程包括了复杂的水解、加氢、氢解、加氢脱氧以及聚合等过程(ChemCatChem 2012,4,64.)。基于此，在贵金属催化剂作用下，木质素转化难以控制在芳醚键断裂步骤，往往伴随苯环加氢等反应发生，得到酚类和烷烃的混合产物，导致原子经济性差。从文献的调研结果看，目前报道的木质素加氢解聚和氧化解聚多以Pd、Pt等贵金属为催化剂，反应条件相对苛刻，通常需要额外添加酸或碱，对环境造成严重污染。
本发明以单原子M1/MoS2(M＝Fe,Ni,Ru,Rh,Pd,Pt,Ir)为催化剂，利用单原子催化剂兼具均相催化剂单一活性位点与多相催化剂稳定、易分离、可重复使用的特点，提高原子利用率，为木质素转化制备芳香化学品提供绿色高效的新途径。
发明内容
单原子M1/MoS2催化剂催化木质素选择解聚制备芳香族化合物的方法，其特征在于：在具有形成氢键能力的溶剂中，单原子催化剂M1/MoS2于氢气条件下催化木质素或木质素模型分子在密闭反应釜中高效解聚制备苯酚基、紫丁香基和愈创木酚基芳香族化合物。
所述木质素为有机木质素、木质素磺酸钠及碱木质素；所述木质素模型分子为具有β-O-4链接的模型化合物。
所述具有形成氢键能力的溶剂为水、甲醇、二氧六环、四氢呋喃、乙醇、正己烷、环己烷、十二烷。
所述反应底物木质素及木质素模型分子与催化剂的质量比为20:1-2:1，室温下反应釜中填充氢气的初始压力为0.7MPa-3MPa；反应温度为150-240 ℃；反应时间为4h–12h。
所述木质素及模型底物原料与催化剂的质量比优选5:1，所述室温下反应釜中填充氢气的初始压力优选为0.7MPa；反应温度优选240℃；反应时间优选为10h。
所述单原子M1/MoS2催化剂为负载型催化剂；M1＝Fe,Ni,Ru,Rh,Pd,Pt,Ir 中的一种，质量负载量为1％-0.5％。
所述负载型单原子M1/MoS2催化剂活性金属的质量负载量优选1％。
与现有技术相比，本发明有如下优点：
1.与现有石油基工业合成路线制备芳香化合物相比，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。
2.本发明为工业木质素如木质素磺酸盐、碱木质素的利用提供了新途径，减少了因工业木质素排放和焚烧所造成的污染。
3.催化剂以单原子铁、镍、钌、铑、钯、铂、铱为主要活性组分，载体MoS2与其协同催化，同时金属负载量低，原子利用率高，活性和选择性高。
4.反应过程中不使用无机酸、碱，避免了木质素降解工艺中常见的环境污染问题。
下面通过具体实施例予以进一步的详细说明。
具体实施方式
实施例1
单原子M1/MoS2催化剂(M＝Fe,Ni,Ru,Rh,Pd,Pt,Ir)的具体制备方法如下：
单原子Ni1/MoS2的制备：四水合钼酸铵0.32g，硫粉0.12g加入到57mL 油胺中室温搅拌10min,随后将0.0145g NiCl3·6H2O充分溶于3mL水中的溶液加入到上述溶液中，室温搅拌1h，然后转入100mL不锈钢反应釜中，升温至220℃反应48h。随后离心过滤，用乙醇和环己烷洗涤数次，直到催化剂表面的配体油胺洗掉得到黑色固体，将收集到的黑色固体真空干燥10 小时。
Fe1,Ru1,Rh1,Pd1,Pt1,Ir1/MoS2的制备:类似Ni1/MoS2的制备过程，分别用 0.014gFeCl3·6H2O,0.0065g RuCl3·H2O,0.0048g PdCl2,0.0061g H2PtCl6,0.0078g H2IrCl6·6H2O代替NiCl3·6H2O。
MoS2的制备：四水合钼酸铵0.32g，硫粉0.12g加入到57mL油胺中室温搅拌10min,将3mL水中的溶液加入到上述溶液中，室温搅拌1h，然后转入100mL不锈钢反应釜中，升温至220℃反应48h。随后离心过滤，用乙醇和环己烷洗涤数次，直到催化剂表面的配体油胺洗掉得到黑色固体，将收集到的黑色固体真空干燥10小时。
纳米Ni/MoS2的制备：将上述合成的MoS2 0.3g分散于四氢呋喃和甲醇的混合液中，然后将溶液置于冰水浴中，加入0.02g NiCl3·6H2O充分搅拌10小时，加入0.15g NaBH4，然后反应24小时，离心分离得到黑色固体，用用乙醇和环己烷洗涤数次，将收集到的黑色固体真空干燥10小时。
纳米Fe,Ru,Rh,Pd,Pt,Ir/MoS2的制备:类似Ni/MoS2的制备过程，分别用0.023gFeCl3·6H2O,0.018g RuCl3·H2O,0.015g PdCl2,0.01g H2PtCl6,0.011g H2IrCl6·6H2O代替NiCl3·6H2O。
实施例2-22单原子M1/MoS2催化剂催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇的解聚反应：在反应釜中将100mg木质素模型分子与单原子M/MoS2催化剂20mg分别溶于30mL甲醇中，用氢气置换六次后于 0.7MPa状态将反应釜密闭并升温至150℃-240℃，以750转/min的速度进行搅拌反应4h-12h。反应结束后，降至室温，上层清液过滤后取样分析。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。反应结果见表1。
表1不同条件下单原子M1/MoS2催化剂和纳米催化剂M/MoS2催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇解聚反应结果
从表中可以看出，所合成的单原子M1/MoS2催化剂都能催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇解聚获得愈创木酚、苯乙烯和乙苯三种芳香化合物，不同催化剂活性有所差别，和MoS2负载的纳米颗粒的催化剂M/MoS2以及单独的MoS2相比较，单原子的催化活性更高。
实施例23-29
Ir1/MoS2在不同条件下催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇的解聚反应：在反应釜中将一定质量的木质素模型分子与单原子催化剂Ir1/MoS2分别溶于30mL不同溶剂中，用氢气置换五次后充入氢气至设定压力，将反应釜升温至240℃，以750转/min的速度进行搅拌反应10h。反应结束后，降至室温，上层清液过滤后取样分析。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。反应结果见表2。
表2不同条件下单原子催化剂Ir1/MoS2催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇解聚反应结果
实施例30-34
单原子催化剂Ir1/MoS2催化不同木质素模型分子的解聚反应：在反应釜中将100mg木质素模型分子(分别记为a-e)与单原子催化剂Ir1/MoS2 20mg 分别溶于30mL甲醇中，用氢气置换五次后于0.7MPa状态将反应釜密闭并升温至240℃，以750转/min的速度进行搅拌反应10h。反应结束后，降至室温，上层清液过滤后取样分析。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。反应式如式1所示：
式1：Ir1/MoS2催化不同β-O-4模型分子反应方程式
反应结果如表3所示。
表3单原子催化剂Ir1/MoS2催化不同木质素模型分子解聚反应结果
从表中可以看出，所合成的单原子Ir1/MoS2催化剂对芳环上具有不同官能团的一系列β-O-4模型化合物都实现了高效解聚。
实施例35-39
在反应釜中将100mg木质素模型分子与单原子催化剂Ir1/MoS2 20mg分别溶于30mL反应溶剂中(分别为乙醇、异丙醇、四氢呋喃、二氧六环、正己烷、水)，用氢气置换五次后于0.7MPa状态将反应釜密闭并升温至240 ℃，以750转/min的速度进行搅拌反应10h。反应结束后，降至室温，上层清液过滤后取样分析。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。结果见表4。
表4.Ir1/MoS2催化木质素模型分子2-(2-甲氧基苯氧基)-1-苯基乙醇在不同溶剂中的反应结果
实施例40-62
真实木质素反应结果
在反应釜中分别加入100mg木质素，20mg催化剂和30mL甲醇，用氮气置换五次后于0.7MPa状态将反应釜密闭并升温至目标反应温度，以750 转/min的速度进行搅拌反应至设定反应时间。反应结束后，降至室温，反应液过滤，滤液50℃旋转蒸发出去溶剂，获得芳香化合物生物油称重计算生物油收率。生物油所包含的组分通过GC-MS联用技术及标样对照进行分析。结果表明生物油中除了愈创木基丙烷、紫丁香基丙烷、愈创木基丙醇及紫丁香基丙醇以外，还包括苯酚、2-甲基苯酚、4-乙基苯酚等C6-C9的酚类化合物。实施例40-62的反应结果见表5。
表5单原子M1/MoS2催化剂和纳米催化剂M/MoS2催化不同木质素解聚活性比较
从表中可以看出，所合成的单原子M1/MoS2催化剂比纳米催化剂 M/MoS2在真实木质素反应实验中表现出更高的活性。结果表明单原子 M1/MoS2催化剂不仅对β-O-4氢解具有高活性，且能高效活化更顽固的β-5 和β-β链接，从而使真实木质素的氢解获得高收率的酚类产物。
Claims (6)
1.一种单原子催化剂在木质素催化加氢制芳香化合物中的应用，采用单原子M1/MoS2催化剂催化木质素选择解聚制备芳香族化合物，其特征在于：在具有形成氢键能力的溶剂中，单原子催化剂M1/MoS2于氢气条件下催化木质素或木质素模型分子在密闭反应釜中高效解聚制备苯酚基、紫丁香基和愈创木酚基芳香族化合物；所述木质素为有机木质素、木质素磺酸钠及碱木质素中的一种或二种以上；所述木质素模型分子为具有ß-O-4链接的模型化合物；反应温度为240 oC；反应时间为10 – 12 h；反应釜中填充氢气的初始压力为0.7 MPa；所述单原子M1/MoS2催化剂为负载型催化剂；M1=Fe, Ni, Ru, Rh, Pd, Pt, Ir中的一种；所述反应底物木质素及木质素模型分子与催化剂的质量比为5:1-2:1。
2.按照权利要求1所述的应用，其特征在于：所述具有形成氢键能力的溶剂为水、甲醇、二氧六环、四氢呋喃、乙醇、正己烷、环己烷、十二烷中的一种或二种以上。
3.按照权利要求1所述的应用，其特征在于：所述木质素及模型底物原料与催化剂的质量比为5:1。
4.按照权利要求1所述的应用，其特征在于：
所述负载型单原子催化剂M1/MoS2活性金属的质量负载量为1%-0.5%。
5.按照权利要求1或4所述的应用，其特征在于：所述负载型单原子催化剂M1/MoS2活性金属的质量负载量为1%。
6.按照权利要求1或4所述的应用，其特征在于：所述负载型单原子催化剂M1/MoS2活性金属的质量负载量0.5%。
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