CN114797969A - 新型多功能聚离子液体催化剂的制备方法及其催化制取木质素基芳香类化合物 - Google Patents
新型多功能聚离子液体催化剂的制备方法及其催化制取木质素基芳香类化合物 Download PDFInfo
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Abstract
本发明属于新材料合成技术领域，公开了规则疏水介孔兼具Brønsted‑Lewis酸性位点的新型多功能聚离子液体催化剂的制备方法及其催化木质素制备芳香族单体。本发明提供的新型多功能聚离子液体催化剂由具有Brønsted‑Lewis酸性离子液体单体、乙烯基修饰的Fe3O4纳米颗粒和具有疏水性的长链羧酸盐阴离子交联剂进行聚合反应制得。其中端烯修饰的Fe3O4纳米颗粒起到骨架强化剂的作用，使新型多功能聚离子液体具备明确的介孔孔道。本发明通过酸性位点、介孔限域和疏水微环境的协同催化作用制得24.6wt%的木质素基芳香单体收率。此催化剂重复使用10次，未发现反应收率明显下降。此催化剂在重质碳资源升级为高附加值化学产品上具有良好的工业化前景。
Description
技术领域
本发明属于新材料合成技术领域，具体涉及制备木质素基芳香族单体的技术领域，尤其涉及一种用于制备木质素基芳香族单体的新型多功能聚离子液体催化剂及其制备方法和应用。
背景技术
芳香族单体是制造各种高附加值化学品的关键原料，目前几乎所有的高附加值化学品都是从不可再生的化石燃料中获得的。随着化石资源的迅速枯竭和对芳香族单体需求的增加，将可再生木质素有效地转化为芳香族单体具有重要意义，同时也带来了许多挑战，如木质素的高交联度和顽拗结构使木质素解聚较为困难。鉴于社会和环境可持续发展，迫切需要开发先进技术将木质素有效地价值化为高附加值化学品。
液体酸催化剂由于其高酸强度、优异的催化活性和酸性位点分布均匀，已被广泛用于许多液体酸催化过程。尽管液体酸催化剂在催化木质素过程中具有很高的催化性能，但同时也会对设备造成严重的腐蚀损坏，并且难以从液体反应混合物中分离。相比之下，固体酸催化剂比液体酸催化剂具有一些优势，例如腐蚀性小、环境友好、安全性高。尤其是与液体酸催化剂相比，固体酸催化剂相对更容易分离和回收。因此，迫切需要开发用于木质素定向转化为芳香族单体的新型固体酸催化剂。
离子液体，尤其是质子型离子液体，作为一种十分重要功能型液体。离子液体的独特的优势是，可以通过设计特定的阴离子部分。金属氯化物阴离子功能化离子液体克服了金属氯化物腐蚀性强、易水解、易失活等缺点。然而，高粘度和低表面积导致的高传质阻力降低了金属氯化物功能化离子液体作为工业应用催化剂的竞争力。聚离子液体也是一种大分子结构，将聚离子液体并入聚合物主链中，有可能解决上述单体中存在的问题。介孔聚离子液体具有可调节的介孔结构和化学成分调节，是一类新型多功能多孔材料，由功能化离子液体、交联剂和其他单体共聚而成。常规方法很难制备规则疏水介孔且兼具Brønsted-Lewis酸性位点聚离子液体催化剂。
发明内容
为克服相关技术中存在的问题，本发明提供了一种用于制备木质素基芳香族单体的新型多功能聚离子液体催化剂及其制备方法和应用。
本发明提供的催化剂是一种高效、环境友好的、具有Brønsted-Lewis酸性部分、明确介孔结构和独特疏水性的新型多功能聚离子液体，其制备方法包括：
1）Brønsted-Lewis酸性位点的离子液体制备方法为：将等摩尔量的1-乙烯基咪唑和1,3-丙磺酸内酯形成所需季铵盐，再使用盐酸酸化得到具备磺酸基团的盐，最后与FeCl3反应。
2）疏水性长链羧酸盐阴离子交联剂制备方法为：摩尔比为1:2的1,2-二溴乙烷和1-乙烯基咪唑加于丙酮中，磁力搅拌，加热回流24h，获得淡黄色固体，通过碱性离子交换树脂进行离子交换。最后，分别使用正丙酸、正己酸和正壬酸酸化。
3）乙烯基修饰的Fe3O4纳米颗粒制备方法为：将Fe3O4纳米颗粒和乙烯基三乙氧基硅烷室温下在乙醇中超声处理2h，然后添加NH3·H2O到混合溶液中将溶液pH值调节至9，然后在80oC下剧烈机械搅拌24h，最终乙醇洗涤3次。
4）新型多功能聚离子液体催化剂制备方法为：将乙烯基改性的Fe3O4纳米颗粒、甲醇、Brønsted-Lewis酸性离子液体、长链羧酸盐阴离子交联剂和偶氮二异丁腈混合于三口烧瓶中，在80oC下剧烈机械搅拌24h，产物使用强磁回收。
5）木质素基芳香族单体制备方法为：将正己烷与新型多功能聚离子液体催化剂和木质素于高压釜中混合，初始氢压为4MPa，反应温度为265oC，反应时间为20h，制备得到木质素基芳香族单体。
在根据本发明的一个实施案例中，所述具备磺酸基团的盐和FeCl3摩尔比为1:0.25-2.25。
在根据本发明的一个实施方案中，所述Brønsted-Lewis酸性离子液体和疏水性长链羧酸盐阴离子交联剂的摩尔比为1:0.5-5。所述引发剂为偶氮二异丁腈。
在根据本发明的一个实施案例中，所述新型多功能聚离子液体催化剂，比表面积为106.81 m2g-1，平均孔直径3.85nm，孔容为0.165cm3g-1。
在根据本发明的一个实施案例中，所述木质素基芳香族单体包括8种单环芳烃或5单环酚类。
在根据本发明的一个实施案例中，所述木质素总转化率49.9%，木质素基芳香族单体的选择性为51.29%（单环芳烃占35.63%，单环酚占15.66%）。
结合上述的所有技术方案，本发明所具备的优点及积极效果为：
1）Brønsted-Lewis离子液体起到活性位点作用，Brønsted-Lewis酸性位点协同促进H2异裂生成H+和H-，然后生成的H+使C-O键裂解生成单环芳香族化合物。
2）端烯修饰的Fe3O4纳米颗粒起到骨架强化剂的作用，使新型多功能聚离子液体具备明确的介孔孔道：明确的介孔孔道增强了H2的吸附量，增加了底物的浓度。
3）具有疏水性的二乙烯基苯片段提供反应过程中所需的疏水微环境：疏水块形成的疏水通道有利于防止Brønsted-Lewis酸性位点的浸出和失活。
4）在催化反应结束后通过新型多功能聚离子液体催化剂磁性回收装置将新型多功能聚离子液体催化剂从反应混合物中分离出来。
5）相对温和的条件下制备木质素基芳香族单体保证实际生产过程中的安全问题，同时将反应设备的耗损降低，
当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本发明的公开。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本公开的实施例，并与说明书一起用于解释本公开的原理。
图1是本发明的一个实施案例中，所述的多功能聚合离子液体的制备流程图。
图2是本发明的一个实施案例中，所述的Brønsted-Lewis酸性离子液体单体分子式。
图3是本发明的一个实施案例中，所述的疏水性长链羧酸盐阴离子交联剂的结构分子式。
图4是本发明实施例提供的新型多功能聚离子液体催化剂制备方法。
图5是本发明实施例提供的通过新型多功能聚离子液体催化剂磁性回收装置：利用外部磁场将新型多功能聚离子液体催化剂从反应混合物中分离出来原理图。
图中：1、外部磁场；2、催化剂；3、固体残渣；4、丙酮。
图6是本发明实施例提供的实施例11和12中使用GC-MS对液体产物进行定性分析，并通过与真实化合物的峰保留时间和质谱进行比较进行鉴定图，其中图6a表示阴离子部分分别为FeCl3和ZrCl2的新型多功能聚离子液体为催化剂时，木质素液体产物中七类物质的选择性。图6b表示阴离子部分为FeCl3时，产物中主要的芳烃和酚类的相对含量。
图7是本发明实施例提供的实施例11中苄基苯基醚加氢裂解的转化率为100%。催化剂重复使用10次，未发现收率明显下降。
图8是使用新型多功能聚离子液体催化剂木质素转化的总离子色谱图中8种单环芳烃与5种单环苯酚的特征峰。
具体实施方式
以下将结合实施例对本发明做进一步说明，本发明的实施例仅用于说明本发明的技术方案，并非限定本发明。
实施例1新型多功能聚离子液体催化剂制备方法：
将乙烯基改性的Fe3O4纳米颗粒（200mg）、甲醇（50ml）、Brønsted-Lewis酸性离子液体（1mmol）、长链羧酸盐阴离子交联剂（2mmol）和偶氮二异丁腈（30mg）混合于三口烧瓶中70 oC强力搅拌24h，产物使用强磁回收，得到了有序多孔的新型多功能聚离子液体催化剂。其比表面积为106.81 m2g-1，平均孔直径3.85nm，孔容为0.165cm3g-1。
实施例2
除了不加乙烯基改性的Fe3O4纳米颗粒，其他反应条件和测定方法均同实施例1，得到了无序无孔的聚离子液体催化剂，其比表面积为0.33 m2g-1，平均孔直径11.37nm，孔容为0.002cm3g-1。
实施例3
在哈氏合金高压釜（100mL）中加入苄基苯基醚（1mmol）、Brønsted和Lewis摩尔比为1：2且Brønsted-Lewis酸性离子液体和烷基链长度为6的长链羧酸盐阴离子交联剂（CLs-C6）摩尔比为1:2时的新型多功能聚离子液体催化剂（100mg）和正己烷（20mL）。在初始氢气压力4MPa、反应温度为265oC、搅拌速度为200rpm和反应时间为3h的条件下进行反应。反应时间结束后，立即将高压釜在冰水浴中迅速冷却。使用GC-MS对液体产物进行定性分析，并通过与真实化合物的峰保留时间和质谱进行比较进行鉴定。苄基苯基醚加氢裂解的转化率为100%。其中产物中苯酚的相对含量为47.33%，甲苯的相对含量为40.65%，苯的相对含量为6.68%，二聚产物的相对含量为5.34%。
实施例4
除了Brønsted和Lewis摩尔比为1：1.5，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为90.17%。其中产物中苯酚的相对含量为44.23%，甲苯的相对含量为42%，苯的相对含量为2.23%，二聚产物的相对含量为11.54%。实施例5
除了Brønsted-Lewis酸性离子液体和烷基链长度为6的长链羧酸盐阴离子交联剂（CLs-C6）1:1，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为83.21%。其中产物中苯酚的相对含量为41.76%，甲苯的相对含量为34.73%，苯的相对含量为7.03%，二聚产物的相对含量为16.48%。
实施例6
除了新型多功能聚离子液体催化剂（80mg），其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为91.23%。其中产物中苯酚的相对含量为46.3%，甲苯的相对含量为41.48%，苯的相对含量为4.82%，二聚产物的相对含量为7.4%。
实施例7
除了初始氢气压力为3MPa，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为80.33%。其中产物中苯酚的相对含量为46.66%，甲苯的相对含量为40.68%，苯的相对含量为5.98%，二聚产物的相对含量为6.68%。
实施例8
除了反应温度为255oC，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为92.34%。其中产物中苯酚的相对含量为46.96%，甲苯的相对含量为41.27%，苯的相对含量为5.69%，二聚产物的相对含量为6.08%。
实施例9
除了反应时间为2h，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为90.27%。其中产物中苯酚的相对含量为47.15%，甲苯的相对含量为41.12%，苯的相对含量为6.03%，二聚产物的相对含量为5.7%。
实施例10
除了Lewis部分为ZrCl2，其他反应条件和测定方法均同实施例3，苄基苯基醚加氢裂解的转化率为98.26%。其中产物中苯酚的相对含量为45.07%，甲苯的相对含量为30.67%，苯的相对含量为14.4%，二聚产物的相对含量为9.86%。
实施例11
在哈氏合金高压釜（100mL）中加入碱木质素（0.2g）、Brønsted和Lewis摩尔比为1：2且Brønsted-Lewis酸性离子液体和烷基链长度为6的长链羧酸盐阴离子交联剂（CLs-C6）摩尔比为1:2时的新型多功能聚离子液体催化剂（100mg）和正己烷（20mL）。在初始氢气压力4MPa、反应温度为265oC、搅拌速度为200rpm和反应时间为20h的条件下进行反应。反应时间结束后，立即将高压釜在冰水浴中迅速冷却。使用GC-MS对液体产物进行定性分析，并通过与真实化合物的峰保留时间和质谱进行比较进行鉴定。其中，木质素总转化率47.9%，木质素基芳香族单体的收率为24.6wt%（单环芳烃占35.6%，单环酚占15.7%）。所述木质素基芳香族单体共有8种单环芳烃和5种单环酚类，其中产物中相对含量最高的单环芳烃和单环酚类分别为甲苯（16.20wt.%）和苯酚（4.74wt.%），具体如图5所示。
实施例12
在哈氏合金高压釜（100mL）中加入苄基苯基醚（1mmol）、Brønsted和Lewis摩尔比为1：2且Brønsted-Lewis酸性离子液体和烷基链长度为6的长链羧酸盐阴离子交联剂（CLs-C6）摩尔比为1:2时的新型多功能聚离子液体催化剂（100mg）和正己烷（20mL）。在初始氢气压力4MPa、反应温度为265oC、搅拌速度为200rpm和反应时间为3h的条件下进行反应。反应时间结束后，立即将高压釜在冰水浴中迅速冷却。使用GC-MS对液体产物进行定性分析，并通过与真实化合物的峰保留时间和质谱进行比较进行鉴定。苄基苯基醚加氢裂解的转化率为100%。催化剂重复使用10次，未发现收率明显下降，具体如图4所示。
需要说明的是，上述发明内容及具体实施方式意在证明本发明所提供技术方案的实际应用，不应解释为对本发明保护范围的限定。本领域技术人员在本发明的精神和原理内，当可作各种修改、等同替换、或改进。本发明的保护范围以所附权利要求书为准。
Claims (9)
1.一种新型多功能聚离子液体催化剂的制备方法，其特征在于：所述新型多功能聚离子液体催化剂由Brønsted-Lewis酸性离子液体、乙烯基修饰的Fe3O4纳米颗粒和具有疏水性的长链羧酸盐阴离子交联剂单体聚合反应制得。
2.如权利要求1所述的Brønsted-Lewis酸性离子液体单体制备方法，其特征在于：将等摩尔量的1-乙烯基咪唑和1,3-丙磺酸内酯形成所需季铵盐，再使用盐酸酸化制得具有磺酸基团的盐，而后与FeCl3反应形成具有Brønsted-Lewis酸性位点的离子液体单体。
3.如权利要求1所述的具有不同Lewis酸性强度的离子液体单体的制备方法，其特征在于：所述具有磺酸基团的盐与FeCl3摩尔比为1:0.25-2.25。
4.如权利要求1所述的具有疏水性的长链羧酸盐阴离子交联剂制备方法，其特征在于：1,2-二溴乙烷和1-乙烯基咪唑溶于丙酮中，而后经磁力搅拌、加热回流24h，获得淡黄色固体，在真空烘箱中干燥8h，而后通过碱性离子交换树脂进行离子交换；最后，分别经过正丙酸、正己酸和正壬酸酸化。
5.如权利要求1所述制备方法，其特征在于：乙烯基修饰的Fe3O4纳米颗粒在介孔聚合离子液体中起到骨架强化剂的作用，其有利于聚合离子液体中规则介孔的形成。
6.如权利要求1所述制备方法，其特征在于，当乙烯基修饰的Fe3O4纳米颗粒参与聚合，交联剂碳链长度为6时，且所述具备Brønsted-Lewis酸性离子液体和长链羧酸盐阴离子交联剂摩尔比为1:3时，获得具有规则疏水介孔且兼具Brønsted-Lewis酸性位点的新型多功能聚离子液体催化剂。
7.如权利要求1所述制备方法所述新型多功能聚离子液体催化剂转化木质素为芳香族单体，其特征在于，将20mL正己烷与0.1g新型多功能聚离子液体催化剂和0.2g木质素于高压釜中混合，初始氢压为4MPa，反应温度为265oC，反应时间为20h，制备得到木质素基芳香族单体。
8.如权利要求7所述制备方法，其特征在于，所述木质素总转化率47.9%，木质素基芳香族单体的收率为24.6wt.%（单环芳烃占35.6%，单环酚占15.7%）。
9.如权利要求7所述制备方法，其特征在于，在催化反应结束后通过新型多功能聚离子液体催化剂磁性回收装置将新型多功能聚离子液体催化剂从反应混合物中分离出来，循环利用。
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