CN106902877B - 一种多酸催化剂及其制备方法和使用方法 - Google Patents
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Abstract
本发明公开了一种用于催化木质纤维素定向转化的多酸催化剂及其制备方法，该催化剂是具有Keggin结构的多酸化合物，以此催化剂催化木质纤维素制备葡糖糖、木糖和草酸醛。催化剂具有高的催化活性、可重复性和广泛的原料适用性，整个制备过程无废水产生，绿色环保。
Description
技术领域
本发明为催化剂制备及应用技术领域，具体涉及一种新的纳米固体多酸催化剂，同时本发明还涉及这种纳米催化剂的制备及其在木质纤维素定向转化方面的应用。
背景技术
进入21世纪，现代社会的发展面临着资源短缺、能源危机和环境恶化等严重问题，化石资源的短缺已经成为全球经济发展的瓶颈因素之一，因此各国都提出相应的发展战略。为了保护环境节约能源人们将目光集中在可再生资源上，生物质材料及能源逐渐浮出水面，从而生物质产业的发展已经成为我国的重要发展战略。生物质在地球上广泛存在，它是利用绿色植物的光合作用所形成的有机物，主要包括糖类(如单糖、淀粉等)、秸秆、木质纤维素、油脂等，因此，生物质是取之不竭用之不尽的资源宝库。
其中，木质纤维素是自然界广泛存在的可再生资源,非食用的木质纤维素包括各种草类、林业加工剩余物、农业废弃物秸秆等。我国是农业大国，木质纤维素资源非常丰富。其中每年产生农作物秸秆约二亿多吨，秸秆已成为一种无用的负担物，秸秆就地焚烧日趋严重，产生的烟雾成为一大社会公害。秸秆的主要成分为纤维、半纤维和木质素，经过水解糖化，纤维素物质可转化为单糖类物质，以此为平台，一方面经化学途径可转化成燃油、燃气及化学品；另一方面通过生物催化可转化成大宗发酵产品及液体生物燃料；其中利用结晶纯化技术得到的单糖晶体更是重要的工业原料。木质纤维素原料制糖(包括葡萄糖和木糖)技术是农作物秸秆利用制备化学品的关键，是后续转化的关键和限制性步骤。
目前国际上采用的预处理方法主要有物理方法(热降解、辐射降解和机械降解)、生物方法(微生物)和化学方法(氧化和水解)。物理方法工艺简单，易于操作，但其降解产物复杂，目标产物难以控制且选择性差。微生物法反应条件温和、环境友好、选择性高、设备简单，随着现代生物研究技术的发展，已经成为当前研究的热点。但生产成本高、制备提纯困难、催化活性和稳定性都较低、反应时间长，而且预处理过程复杂，至今仍难以实现大规模工业应用。化学法包括氧化降解和水解。传统的无机酸如H2SO4预处理是目前广泛使用的预处理方法，在高温(170-240℃)和高压条件下，它能够释放大多数的戊糖，并能提高纤维素的水解效果。但半纤维素在此条件下分解成木糖，木糖不耐高温高压继续降解形成发酵抑制物糠醛；同时单次处理对木质素的去除率较低，在20％以内；产品需要脱酸处理产生大量废水。造成高能耗、设备腐蚀、工艺复杂、大量废酸及环境污染等问题，已成为制约纤维素规模化生产的技术瓶颈。NaOH、KOH碱性预处理与酸及其它氧化剂相比，在不降解半纤维素聚合体的情况下，更有利于打破木质素、半纤维素和纤维素之间的酯键，但较高的成本和脱碱处理限制了该方法的大规模使用。氧化预处理是利用湿法氧化(Wetoxidation)技术在高温水蒸汽和高压氧气共同存在下氧化木质纤维素原料，使部分木质素和大多数半纤维素溶解，但仍然存在高消耗和设备高成本问题。
多金属氧酸盐(POMs，也被称为多酸HPAs)，同时具有良好的酸性和氧化还原性，是一类在工业中有重大应用的酸和氧化还原催化剂。与传统的催化剂硫酸等相比，具有无毒、无污染的特点，是绿色环保型固体酸型和氧化型催化剂。在众多POMs中，Keggin型含钛多酸H3+2x[PW12-xTixO40](x＝1-3)被应用于氧化反应中，具有良好的催化氧化能力和一定的酸性能，在众多的有机反应中使用。在催化木质纤维素定向转化中的使用，目前没有报道。
发明内容
为了克服现有技术的不足，本发明提供一种用于催化木质纤维素定向转化的多酸催化剂及其制备方法,以及多酸催化剂在木质纤维素定向转化中的使用方法。
本发明解决技术问题采用的技术方案是：
一种用于催化木质纤维素定向转化的多酸催化剂，是具有Keggin结构的多酸化合物，该多酸化合物的通式为：
[C16H33N(CH3)3]3+2x[PW12-xTixO40](x＝1、2、3)
一种用于催化木质纤维素定向转化的多酸催化剂，其制备方法如下：
按摩尔比1：0-5分别称取多酸化合物K3+2x[PW12-xTixO40]·6H2O和表面活性剂[C16H33(CH3)3N]Br；把多酸化合物K3+2x[PW12-xTixO40]·6H2O倒入反应器中，加入质量比为1：5-10倍的蒸馏水，加热到50-70℃，搅拌溶解；再向其中加入表面活性剂，反应液陈化5-10小时，析出白色固体物，过滤，用蒸馏水冲洗沉淀2-3次，直到洗出液的pH值达到5-8，得到沉淀物；将该沉淀物置于马弗炉中，于150-300℃烧结2-6小时，即得到一种木质纤维素定向转化的多酸催化剂。
一种多酸催化剂在木质纤维素定向转化中的使用方法如下：
将木质纤维素、催化剂、水按照一定比例(1:4.5:70)加入到高压反应器中，设定反应温度80～140℃，反应时间5～10小时，使得木质纤维素转化为葡萄糖、木糖和香草醛。催化剂的用量10～50mg。反应结束后，离心分离出催化剂和未反应的木质纤维，重复转化。产物用甲基异丁基酮萃取两次，有机相40℃减压蒸馏蒸出甲基异丁基酮，得到产品香草醛；水相用乙醇萃取，乙醇相40℃减压蒸馏蒸出乙醇得到葡萄糖；剩余水相50℃减压蒸馏蒸出水得到木糖。
本发明的有益效果是：
利用Keggin结构的多酸作为催化剂可以在木质纤维素定向过程中解决很多技术性难题：
1、Keggin结构的多酸含有Ti和W，具有高氧化能力，同时由于存在Lewis酸中心，催化剂具有一定的酸性能，可以满足酸/氧化双重预处理分离木质素、纤维素和半纤维素的需要，实现木质纤维定向转化为葡萄糖、木糖和香草醛；
2、POMs体系是酸/氧化双重中心的固体催化剂。在木质纤维素反应体系中为非均相催化剂，易于从反应体系分离出来，再生方法简便，不产生大量污水，降低催化剂使用成本。
3、POMs固体催化剂在水体系中自组装形成“纳米体系”，提高催化剂的比表面积，来提高催化剂的催化活性。催化剂转化效率高。
4、POMs一步法处理木质纤维素，操作简单，不需要中间产物的分离过程，制备成本低，且绿色、无氧化剂的二次污染。
通过设计合成不同组成的多酸催化剂，可以满足木质纤维素定向转化制备葡萄糖、木糖和香草醛的需要，实用性强。
具体实施方式
实施例一
分别称取摩尔比1：4多酸化合物K5[PW11TiO40]·6H2O和表面活性剂[C16H33(CH3)3N]Br；把多酸化合物K5[PW11TiO40]6H2O倒入反应器中，加入质量比为6倍的蒸馏水，加热到60℃，搅拌溶解；再向其中加入表面活性剂，反应液陈化7小时，析出白色固体物，过滤，用蒸馏水冲洗沉淀3次，直到洗出液的pH值达到7.1，得到沉淀物；将该沉淀物置于马弗炉中，于170℃烧结2小时，即得到一种木质纤维素定向转化的多酸催化剂，其产率为50％。
实施例二
将木质纤维素1g，30mg[C16H33(CH3)3N]5[PW11TiO40]·6H2O的催化剂放入高压反应器中，加入6mL的去离子水，加热搅拌。反应温度为100℃，反应时间为8小时。反应结束后，冷却后将反应混合物放入离心管中进行离心分离，清液中包含产物葡萄糖、木糖和香草醛，沉淀中是没有反应的木质纤维素和催化剂。产物用甲基异丁基酮萃取两次，有机相40℃减压蒸馏蒸出甲基异丁基酮，得到产品香草醛；水相用乙醇萃取，乙醇相40℃减压蒸馏蒸出乙醇得到葡萄糖；剩余水相50℃减压蒸馏蒸出水得到木糖；产率分别为45％，30％和61％。
Claims (2)
1.一种用于催化木质纤维素定向转化的多酸催化剂，
所述多酸催化剂是具有Keggin结构的多酸化合物，该多酸化合物的通式为：
[C16H33N(CH3)3]3+2x[PW12-xTixO40]，其中，x＝1、2、3；其制备方法如下：
按摩尔比1：0-5分别称取多酸化合物K3+2x[PW12-xTixO40]·6H2O和表面活性剂[C16H33(CH3)3N]Br，其中，表面活性剂的摩尔量不取0；把多酸化合物K3+2x[PW12-xTixO40]·6H2O倒入反应器中，加入质量比为1：5-10倍的蒸馏水，加热到50-70℃，搅拌溶解；再向其中加入表面活性剂，反应液陈化5-10小时，析出白色固体物，过滤，用蒸馏水冲洗沉淀2-3次，直到洗出液的pH值达到5-8，得到沉淀物；将该沉淀物置于马弗炉中，于150-300℃烧结2-6小时，获得多酸催化剂，用于催化木质纤维素定向转化为葡萄糖、木糖和香草醛。
2.一种权利要求1所述多酸催化剂在木质纤维素定向转化中的使用方法，其特征在于：
将木质纤维素、权利要求1所述的多酸催化剂和水按照质量比例1:4.5:70加入到高压反应器中，反应温度80～140℃，反应时间5～10小时，使木质纤维素转化为葡萄糖、木糖和香草醛，催化剂用量10～50mg；反应结束后，离心分离出催化剂和未反应的木质纤维，重复转化；产物用甲基异丁基酮萃取两次，有机相40℃减压蒸馏蒸出甲基异丁基酮，得到产品香草醛；水相用乙醇萃取，乙醇相40℃减压蒸馏蒸出乙醇得到葡萄糖；剩余水相50℃减压蒸馏蒸出水得到木糖。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406848A (zh) * | 2008-11-24 | 2009-04-15 | 东北师范大学 | 高分散固载Keggin型多金属氧酸盐晶态催化剂的制备方法 |
| CN102575301A (zh) * | 2010-01-27 | 2012-07-11 | 科学与工业研究委员会 | 将木质纤维素转化为增值化学品的一锅单步水解方法 |
| CN104900410A (zh) * | 2014-12-18 | 2015-09-09 | 北京工商大学 | 磷钨钛杂多配合物与半菁染料杂化的光电转换薄膜及其传感性质 |
| CN105080608A (zh) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | 一种新型多酸催化剂在纤维素水解中的应用 |
| CN105080607A (zh) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | 一种催化制备氧化淀粉的多酸催化剂 |
-
2016
- 2016-11-04 CN CN201610966044.9A patent/CN106902877B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406848A (zh) * | 2008-11-24 | 2009-04-15 | 东北师范大学 | 高分散固载Keggin型多金属氧酸盐晶态催化剂的制备方法 |
| CN102575301A (zh) * | 2010-01-27 | 2012-07-11 | 科学与工业研究委员会 | 将木质纤维素转化为增值化学品的一锅单步水解方法 |
| CN105080608A (zh) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | 一种新型多酸催化剂在纤维素水解中的应用 |
| CN105080607A (zh) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | 一种催化制备氧化淀粉的多酸催化剂 |
| CN104900410A (zh) * | 2014-12-18 | 2015-09-09 | 北京工商大学 | 磷钨钛杂多配合物与半菁染料杂化的光电转换薄膜及其传感性质 |
Non-Patent Citations (3)
| Title |
|---|
| Ti（Ⅳ）取代的Keggin型多金属氧酸盐的合成及其在水溶液中的行为;刘红霞等;《南京师大学报(自然科学版)》;20070630;第30卷(第2期);第63页第1段 |
| Ti2W10PO407- and [CpFe(CO)2Sn]2W10PO385- Preparation, properties, and structure determination by tungsten-183 NMR;P.J.Domaille等;《Inorg. Chem.》;19830331;第22卷(第5期);第818-822页 |
| 固体杂多酸催化剂设计与合成在纤维素水解反应中的应用;程明星;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20130515(第5期);第18页第1段-第19页最后一段，第20页"3.纤维素水解制备单糖"，第36-40页"3.影响纤维素水解制备葡萄糖的因素" |
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