CN114369842A - 一种羰基化合物催化加氢装置及其应用 - Google Patents
一种羰基化合物催化加氢装置及其应用 Download PDFInfo
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Abstract
本发明属于羰基化合物加氢领域,具体涉及一种羰基化合物催化加氢装置及其应用。为解决羰基化合物催化加氢反应的油水混合体系中,存在羰基化合物分子与H自由基接触困难、光催化产生的H自由基速率难以调控的问题,提供了一种含有光电催化复合膜的装置,能够以水为氢源,实现光电催化产氢与原位羰基化合物催化加氢反应的连串反应装置。装置包括光电催化复合膜、由光电催化复合膜分割成的阳极室和阴极室、阳极和阴极。以光电催化复合膜作为阳极室和阴极室的隔膜,阳极室加入电解质水溶液,阴极室加入羰基化合物有机溶液,在氙灯光照和外加电压下,进行光电催化羰基化合物加氢反应。
Description
技术领域
本发明属于羰基化合物加氢领域,具体涉及一种羰基化合物催化加氢装置及其应用。
背景技术
醇类化合物是人们生活中常见的物质,也是重要的化工原料,将羰基化合物还原为醇类化合物是工业合成中重要的反应。关于醛酮还原成醇的报道很多,其中,催化加氢化法是较为常见的还原羰基的方法。然而,目前的加氢还原反应体系中,主要采用H2作为氢源,需要在高温高压下进行,具有较大的安全隐患,而且能耗较大。还有一些报道采用NaBH4、水合肼、NH3BH3、HCOOH、醇、烷烃等作为氢源,但往往成本较高,而且会产生副产物,容易造成环境污染。
水作为地球上最广泛使用的溶剂和氢来源具有压倒性优势,如无毒和低成本,因此可能是有机氢供体的理想选择。但由于水分子稳定,难以被激活和脱氢,很少用于转移氢化反应,如何使水活化生成氢是一个巨大挑战。近年来,一些研究人员试图以水作为氢源,通过设计高效的双功能催化剂,将光催化产生的H自由基随后与羰基化合物发生原位加氢反应。但在传统使用的油水混合体系中,亲水性的催化剂表面通常被水分子包围,使羰基化合物分子与H自由基接触困难,从而导致羰基化合物加氢效率大大降低。此外,传统方法直接将光催化剂粉末加入到油水混合体系,光催化产生的H自由基速率难以调控,速率太快会导致析H2反应加剧,速率太慢导致羰基化合物加氢反应的氢源不足。因此,如何使羰基化合物分子与H自由基有效接触,并且能够有效调控H自由基产生速率是当前最具挑战性的障碍。
发明内容
本发明为解决现有技术中羰基化合物催化加氢反应的油水混合体系中,存在羰基化合物分子与H自由基接触困难、光催化产生的H自由基速率难以调控的问题,提供一种含有光电催化复合膜的装置,能够以水为氢源,实现光电催化产氢与原位羰基化合物加氢反应的连串反应装置及应用。
为了达到上述目的,本发明采用了下列技术方案:
一种羰基化合物催化加氢装置,反应器、光电催化复合膜、阴极、阳极、光源和直流电源;所述光电催化复合膜设置在反应器内,将反应器分为阳极室和阴极室,所述阴极和阳极分别设置在阴极室和阳极室内,所述直流电源的正极和负极分别与阳极和阴极连接,所述光源设置在阴极室的上方;
所述光电催化复合膜由双极膜和表面负载光电催化剂的疏水膜构成,双极膜是由阴离子交换膜和阳离子交换膜复合而成,所述阳极室为电解质水溶液,阴极室为羰基化合物有机溶液,所述光源为氙灯。
进一步,所述光电复合膜的制备方法如下:
(1)采用聚乙烯醇、聚吡咯烷酮、聚砜、聚苯醚、聚乙烯苄基氯中的一种或几种任意比例的混合物作为阴离子交换膜的支撑,采用一种或几种按任意比混合的含有伯氨基、仲氨基、叔氨基或季氨基的化合物作为阴离子交换膜的固定基团,加入戊二醛溶液作为交联剂,配制阴离子交换膜液,通过流延法制备阴离子交换膜;
(2)采用聚乙烯醇、聚乙烯吡咯烷酮、聚苯醚、聚砜和苯乙烯中的一种或几种任意比例的混合物作为阳离子交换膜的支撑,采用一种或几种按任意比混合的含有磺酸基、羧酸基或磷酸基的化合物作为阳离子交换膜的固定基团,加入FeCl3或CaCl2溶液作为交联剂,配制阳离子交换膜液,流延于步骤(1)制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂负载于疏水性材料表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水膜。
进一步,所述光催化剂为Pt/C3N4、Pt/TiO2、Pt/MoS2、Pd/C3N4、Pd/TiO2、Pd/MoS2、Pd-Pt/TiO2、Pd-Pt/C3N4、Pd-Pt/MoS2中的一种。
进一步,所述疏水性材料为碳纤维、碳纳米管、疏水介孔SiO2、疏水分子筛、疏水金属有机框架材料中的一种。
进一步,所述直流电源的电压为0.3~2.5V;所述电解质水溶液为Na2SO4溶液、NaOH溶液或KOH溶液中的一种,浓度为0.01~3.0mol L-1;所述羰基化合物有机溶液包括对溴苯甲醛、对氯苯甲醛、二苯甲酮、糠醛、对甲苯醛溶液,溶剂为辛烷、庚烷或己烷。
一种羰基化合物催化加氢装置的应用,应用于羰基化合物加氢。
与现有技术相比本发明具有以下优点:
(1)本发明利用双极膜水解离技术为光催化提供氢离子,在电场驱动力作用下,氢离子透过阳离子交换膜迁移到疏水膜表面,与光电催化剂接触并被光生电子还原为零价氢,然后零价氢与羰基化合物在金属催化剂作用下进行原位加氢反应;因此,通过调控双极膜水解离速率,进而控制光催化产生H自由基速率,避免速率太快导致析H2反应加剧,速率太慢导致羰基化合物加氢反应的氢源不足。
(2)本发明疏水膜表面为纤维状、管状、多孔状疏水性材料,有利于疏水性的羰基化合物分子进入催化剂表面发生反应,解决了传统油水两相混合体系中,羰基化合物分子难以到达催化剂表面与H自由基接触的问题。
(3)本发明通过外加电压使光电催化复合膜两侧形成电场,一方面有利于促进光生电子-空穴的有效分离,提高光电催化效率,另一方面电场作用对氢离子、H自由基的定向迁移具有促进作用,有利于羰基化合物加氢反应进行。
(4)本发明疏水膜可有效阻止阳极室水溶液进入阴极室,从而有效阻止水分子进入阴极室发生析氢反应。
(5)本发明利用膜液具有粘性的特征,将负载有光催化剂的疏水膜材料流延于阳离子膜表面,不仅有效避免了传统方法将催化剂粉末直接加入到油水双相体系而发生团聚现象,而且便于循环回收再利用。
(6)本发明双极膜中间界面层水解离消耗的水,由阳极室电解质水溶液中的水透过阴离子交换膜进行补充。
附图说明
图1是本发明羰基化合物加氢装置示意图;
图2是将双极膜在液氮中脆断后的截面SEM图;
图3是本发明实施例1制备阳离子交换膜采用FeCl3溶液交联示意图;
图4是本发明实施例1制备的MoS2光催化剂的形貌图。
具体实施方式
实施例1
如图1所示,一种羰基化合物催化加氢装置,包括反应器、光电催化复合膜、阴极、阳极、光源和直流电源;所述光电催化复合膜设置在反应器内,将反应器分为阳极室和阴极室,所述阴极和阳极分别设置在阴极室和阳极室内,所述直流电源的正极和负极分别与阳极和阴极连接,所述光源设置在阴极室的上方;
所述光电催化复合膜由双极膜和表面负载光电催化剂的疏水膜构成,双极膜是由阴离子交换膜和阳离子交换膜复合而成,所述阳极室为电解质水溶液,阴极室为羰基化合物有机溶液,所述光源为氙灯。
光电催化复合膜的制备方法如下:
(1)将质量相等的聚乙烯醇和壳聚糖混合后倒入烧杯,加入质量分数为0.01%的醋酸水溶液,在60℃恒温水浴锅中不断搅拌,完全溶解后加入戊二醛,继续搅拌1h,静置脱泡后,流延于平整干洁的带边框玻璃板上,放入鼓风干燥箱中烘干,得到阴离子交换膜;
(2)将质量相等的聚乙烯醇和羧甲基纤维素钠混合后倒入烧杯,搅拌下加入去离子水,加热到60℃溶解,待完全溶解后加入FeCl3溶液,继续搅拌1h,静置脱泡后,流延于上述制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂Pt/MoS2负载于疏水性碳纤维表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水性膜;
以光电催化复合膜作为阳极室和阴极室的隔膜,阳极室加入浓度为0.01mol L-1的Na2SO4电解质水溶液,阴极室加入含有0.18mmol对溴苯甲醛的辛烷溶液,在氙灯光源照射下,直流电源电压为1.0V下,进行光电催化对溴苯甲醛加氢反应。反应3小时后,从阴极室取样检测,测得对溴苯甲醛的转化率为99.1%。
图2是将双极膜在液氮中脆断后的截面SEM图,从图中可以清晰看到构成双极膜的阴离子交换膜和阳离子交换膜,以及两膜层之间的中间界面层。双极膜中间界面层的厚度通常只有纳米级厚度,因此,即使在双极膜两侧施加很小的电压,双极膜中间界面层也可以形成强大的电场,在强大的电场作用,双极膜中间界面层的水分子即可发生水解离。
图3是采用FeCl3溶液交联阳离子交换膜的示意图,从图中可以看出,通过FeCl3溶液交联后,阳离子交换膜形成网状结构,有利于提高膜的机械性能,从而可提高膜的使用寿命。
图4是制备的MoS2光催化剂的形貌图,从图中可以看出,MoS2光催化剂呈现单层或少层的片层结构,有利于提高光生载流子的分离效率,从而提高光电催化效率。
实施例2
与实施例1的区别在于光电催化复合膜的制备方法不同,具体步骤如下:
(1)将质量比为2:1的聚吡咯烷酮和季铵聚砜混合后倒入烧杯,加入质量分数为0.02%的醋酸水溶液,在50℃恒温水浴锅中不断搅拌,完全溶解后加入戊二醛,继续搅拌1h,静置脱泡后,流延于平整干洁的带边框玻璃板上,放入鼓风干燥箱中烘干,得到阴离子交换膜;
(2)将质量相等的聚乙烯吡咯烷酮和磷酸纤维素混合后倒入烧杯,搅拌下加入去离子水,加热到60℃溶解,待完全溶解后加入CaCl2溶液,继续搅拌1h,静置脱泡后,流延于上述制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂Pd/TiO2负载于疏水性碳纳米管表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水性膜。
以光电催化复合膜作为阳极室和阴极室的隔膜,阳极室加入浓度为0.03mol L-1的K2SO4电解质水溶液,阴极室加入含有0.25mmol对氯苯甲醛的庚烷溶液,在氙灯光源照射下,直流电源电压为1.2V下,进行光电催化对氯苯甲醛加氢反应。反应2.5小时后,从阴极室取样检测,测得对氯苯甲醛的转化率为98.7%。
实施例3
与实施例1的区别在于光电催化复合膜的制备方法不同,具体步骤如下:
(1)将质量比为3:1的聚苯醚和聚酰亚胺混合后倒入烧杯,加入质量分数为0.03%的醋酸水溶液,在60℃恒温水浴锅中不断搅拌,完全溶解后加入戊二醛,继续搅拌1.5h,静置脱泡后,流延于平整干洁的带边框玻璃板上,放入鼓风干燥箱中烘干,得到阴离子交换膜;
(2)将质量相等的聚乙烯吡咯烷酮和磺酸基纤维素混合后倒入烧杯,搅拌下加入去离子水,加热到70℃溶解,待完全溶解后加入CaCl2溶液,继续搅拌1h,静置脱泡后,流延于上述制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂Pt/C3N4负载于疏水分子筛表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水性膜。
以光电催化复合膜作为阳极室和阴极室的隔膜,阳极室加入浓度为3.0mol L-1的KOH电解质水溶液,阴极室加入含有0.30mmol二苯甲酮的己烷溶液,在氙灯光源照射下,直流电源电压为2.5V下,进行光电催化二苯甲酮加氢反应。反应3.5小时后,从阴极室取样检测,测得二苯甲酮的转化率为99.4%。
实施例4
与实施例1的区别在于光电催化复合膜的制备方法不同,具体步骤如下:
(1)将质量比为0.5:1的聚砜和甘油基三甲基氯化铵混合后倒入烧杯,加入质量分数为0.005%的醋酸水溶液,在70℃恒温水浴锅中不断搅拌,完全溶解后加入戊二醛,继续搅拌2.5h,静置脱泡后,流延于平整干洁的带边框玻璃板上,放入鼓风干燥箱中烘干,得到阴离子交换膜;
(2)将质量相等的聚乙烯吡咯烷酮和醋酸纤维素混合后倒入烧杯,搅拌下加入质量分数为0.05%的磷酸水溶液,加热到70℃溶解,待完全溶解后加入FeCl3溶液,继续搅拌1h,静置脱泡后,流延于上述制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂Pd-Pt/C3N4负载于疏水介孔SiO2表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水性膜。
以光电催化复合膜作为阳极室和阴极室的隔膜,阳极室加入浓度为0.01mol L-1的NaOH电解质水溶液,阴极室加入含有0.35mmol对甲苯醛的辛烷溶液,在氙灯光源照射下,直流电源电压为0.8V下,进行光电催化对甲苯醛加氢反应。反应5.0小时后,从阴极室取样检测,测得对甲苯醛的转化率为99.4%。
Claims (6)
1.一种羰基化合物催化加氢装置,其特征在于,所述加氢装置包括反应器、光电催化复合膜、阴极、阳极、光源和直流电源;所述光电催化复合膜设置在反应器内,将反应器分为阳极室和阴极室,所述阴极和阳极分别设置在阴极室和阳极室内,所述直流电源的正极和负极分别与阳极和阴极连接,所述光源设置在阴极室的上方;
所述光电催化复合膜由双极膜和表面负载光电催化剂的疏水膜构成,双极膜是由阴离子交换膜和阳离子交换膜复合而成,所述阳极室为电解质水溶液,阴极室为羰基化合物有机溶液,所述光源为氙灯。
2.根据权利要求1所述的一种羰基化合物催化加氢装置,其特征在于,所述光电复合膜的制备方法如下:
(1)采用聚乙烯醇、聚吡咯烷酮、聚砜、聚苯醚、聚乙烯苄基氯中的一种或几种任意比例的混合物作为阴离子交换膜的支撑,采用一种或几种按任意比混合的含有伯氨基、仲氨基、叔氨基或季氨基的化合物作为阴离子交换膜的固定基团,加入戊二醛溶液作为交联剂,配制阴离子交换膜液,通过流延法制备阴离子交换膜;
(2)采用聚乙烯醇、聚乙烯吡咯烷酮、聚苯醚、聚砜和苯乙烯中的一种或几种任意比例的混合物作为阳离子交换膜的支撑,采用一种或几种按任意比混合的含有磺酸基、羧酸基或磷酸基的化合物作为阳离子交换膜的固定基团,加入FeCl3或CaCl2溶液作为交联剂,配制阳离子交换膜液,流延于步骤(1)制备的阴离子交换膜表面,得到阳离子交换膜;
(3)将光电催化剂负载于疏水性材料表面,然后超声分散于水溶液或者无水乙醇中,流延于阳离子交换膜表面,得到负载光电催化剂的疏水膜。
3.根据权利要求2所述的一种羰基化合物催化加氢装置,其特征在于,所述光电催化剂为Pt/C3N4、Pt/TiO2、Pt/MoS2、Pd/C3N4、Pd/TiO2、Pd/MoS2、Pd-Pt/TiO2、Pd-Pt/C3N4、Pd-Pt/MoS2中的一种。
4.根据权利要求2所述的一种羰基化合物催化加氢装置,其特征在于,所述疏水性材料为碳纤维、碳纳米管、疏水介孔SiO2、疏水分子筛、疏水金属有机框架材料中的一种。
5.根据权利要求1所述的一种羰基化合物催化加氢装置,其特征在于,所述直流电源的电压为0.3~2.5V;所述电解质水溶液为Na2SO4溶液、NaOH溶液或KOH溶液中的一种,浓度为0.01~3.0mol L-1;所述羰基化合物有机溶液包括对溴苯甲醛、对氯苯甲醛、二苯甲酮、糠醛、对甲苯醛溶液,溶剂为辛烷、庚烷或己烷。
6.一种权利要求1所述的羰基化合物催化加氢装置的应用,其特征在于,应用于羰基化合物加氢。
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