CN107159174A - 一种钛酸纳米纤维的制备方法及其催化果糖的应用 - Google Patents
一种钛酸纳米纤维的制备方法及其催化果糖的应用 Download PDFInfo
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract
本发明公开了一种催化果糖脱水生成5‑羟甲基糠醛(5‑HMF)的催化剂,该催化剂是由水热法合成的钛酸纳米纤维,显著提高了果糖转化生成5‑羟甲基糠醛的产率。在以二甲基亚砜(DMSO)为溶剂,钛酸纳米纤维作为催化剂,在140℃下催化果糖5小时,5‑羟甲基糠醛的产率可以达到77.4%,是一种具有定向选择性功能的高效催化剂。本发明催化剂的制作成本低、制备方法简单,且能够重复利用。
Description
技术领域
本发明涉及了纤维状的钛酸纳米材料固体催化剂的制备方法及其催化果糖的应用。
背景技术
在过去的一个多世纪,人类的能源主要来自于化石资源,例如石油、煤和天然气。然而,不断增长的能源需求、化石能源储量的减少及其带来的环境问题迫使我们不得不探索新能源。5-羟甲基糠醛(5-HMF)作为重要的平台化合物,经过发生加氢、水解、卤化、酯化等一系列反应可以合成多种化学中间体及燃料,广泛用于化工及能源等领域,是我们解决能源危机的一个突破口。
5-HMF主要来源于多糖、低聚糖及单糖的转化,糖在自然界中广泛存在,也是生物质的主要成分。生物质作为一种可持续性资源,具有来源广泛、储备量巨大、价格低廉、可被生物降解等优点。因此,生物质能成为非常理想的替代资源而受到广泛的关注。单糖(如葡萄糖、果糖等)通常在溶剂中经催化剂作用脱水生成5-HMF。众所都知,葡萄糖脱水生成5-HMF首先要异构化生成果糖,故由葡萄糖合成5-HMF一般产率比较低,相比而言果糖相对较容易生成5-HMF。
目前,主要通过研究催化剂及溶剂来提高果糖转化生成5-HMF效率。固体酸催化剂具有可重复利用、易于分离、绿色环保等优点,因而在5-HMF的制备过程中有非常广阔的前景。钛酸纳米材料具有较多的酸性位点且易于制备,适用于催化果糖制备5-HMF,同时众多研究表明DMSO作为溶剂可以有效抑制5-HMF转化为其他副产物。
发明内容
本发明提供了具有纤维状的钛酸纳米材料固体催化剂的制备方法,并应用于催化果糖转化为5-羟甲基糠醛且具有较高的催化效率及循环催化性能。
本发明制备过程简单,原料易得,不需要昂贵设备,所得产品具有较好的催化性能,可以高效催化果糖转化为5-羟甲基糠醛。
本发明中制备的催化剂成本低、转化率高,是一种具有定向选择性功能的高效催化剂,难得的是可以回收循环使用,可以快速、高效、循环催化果糖转化为5-羟甲基糠醛。
本发明的技术方案是提供一种可用作催化果糖转化为5-羟甲基糠醛的催化剂钛酸纳米纤维,其制备方法包括以下步骤:
1)TiO2(325目)加入到10mol/L NaOH溶液中,将上述混合溶液超声30分钟,然后再搅拌1小时;
2)用聚四氟乙烯内衬的水热反应釜装步骤1)中的混合物,进行水热反应,180℃,反应48小时;
3)用去离子水将步骤2)中反应后的沉淀洗至中性;
4)将步骤3)中得到的沉淀浸没在0.1mol/L HCl溶液中2小时,然后再搅拌1小时;
5)用去离子水将步骤4)得到的沉淀洗至中性,之后80℃下真空干燥12小时,得到钛酸纳米纤维催化剂;
6)将5)得到的固体用于催化果糖生成5-HMF,以DMSO为溶剂,140℃反应5小时并利用高效液相测定其产率。
本发明具有以下优点:
本发明使用的原料主要是二氧化钛和氢氧化钠,来源广泛,价格便宜,转化成特定形貌催化剂的转化率高。
本发明方法制备的催化剂为高效催化剂,在以DMSO为溶剂,钛酸纳米纤维作为催化剂,在140℃下催化果糖反应时间为5小时,5-羟甲基糠醛的产率可以达到77.4%。
本发明方法制备的催化剂为异相固体催化剂具有易分离性,反应完后可经过过滤洗涤等简单操作从反应体系中分离出来。
本发明方法制备的催化剂的循环催化性能很好,简单分离、清洗、干燥后即可重复利用,催化效率基本不变,可以多次回收利用。
本发明方法制备的催化剂可大量合成,不需要昂贵设备。
附图说明
图1是具体实施例1得到的钛酸纳米纤维催化剂的SEM和TEM图;
图2是具体实施例1得到的钛酸纳米纤维在不同反应时间下催化果糖生成5-HMF的产率;
图3是具体实施例1得到的钛酸纳米纤维催化果糖生成5-HMF的循环催化能力。
具体实施方式
以下结合具体实施例,对本发明进行详细说明。
实施例1
5g TiO2(325目)加入到70mL 10mol/L NaOH溶液中,将上述混合溶液超声30分钟,然后再搅拌1小时;
将搅拌均一的反应液倒入聚四氟乙烯为内衬的水热反应釜中后拧紧,烘箱温度调至180℃,温度稳定至180℃后,将水热釜放入烘箱,反应时间为48小时。
将水热反应后的沉淀收集后用二次水洗至pH~7,将白色沉淀浸没在500mL0.1mol/L HCl溶液中2小时,然后再搅拌1小时。
用二次水将上述得到的沉淀洗至pH~7,之后80℃下真空干燥12小时,得到钛酸(H2Ti3O7)纳米纤维;
将上述所得到的固体催化剂用于催化果糖转化生成5-HMF的反应,以DMSO为溶剂,在140℃下反应不同时间,最终产物用高效液相色谱测量其产率,表征此种异相催化剂的催化性能。
催化反应结束后,将催化剂从反应体系中经离心分离出来,得到的固体用DMSO洗三次,再用乙醇洗三次,在120℃下干燥5小时,将得到的固体再次用于相同的催化反应,考察其循环催化性能。
应当理解的是,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (4)
1.一种钛酸纳米纤维的制备方法及其催化果糖的应用:
1)TiO2(325目)加入到10mol/L NaOH溶液中,将上述混合溶液超声30分钟,然后再搅拌1小时;
2)用聚四氟乙烯内衬的水热反应釜装步骤1)中的混合物,进行水热反应;
3)用去离子水将步骤2)中反应后的沉淀洗至中性;
4)将步骤3)中得到的固体浸没在0.1mol/L HCl溶液中,然后再搅拌1小时;
5)用去离子水将步骤4)得到的沉淀洗至中性,之后进行烘干,得到钛酸纳米纤维催化剂;
6)将5)得到的固体用于催化果糖生成5-HMF。
2.根据权利要求1所述的制备方法,其特征是,步骤2)中所述的水热条件为180℃,反应时间是48小时。
3.根据权利要求1所述的制备方法,其特征是,步骤5)中所述的干燥条件为80℃下真空干燥,干燥时间为12小时。
4.根据权利要求1所述的制备方法,其特征是,步骤6)中所述的催化条件是溶剂为DMSO,反应温度为140℃,反应时间为5小时。
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Cited By (2)
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CN108706677A (zh) * | 2018-05-21 | 2018-10-26 | 大连理工大学 | 一种过氧化氢增强光催化膜分离性能的方法 |
CN108931569A (zh) * | 2018-06-28 | 2018-12-04 | 海南师范大学 | 一种血红蛋白和钛酸纳米纤维修饰碳离子液体电极的制备及其电化学分析应用 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108706677A (zh) * | 2018-05-21 | 2018-10-26 | 大连理工大学 | 一种过氧化氢增强光催化膜分离性能的方法 |
CN108931569A (zh) * | 2018-06-28 | 2018-12-04 | 海南师范大学 | 一种血红蛋白和钛酸纳米纤维修饰碳离子液体电极的制备及其电化学分析应用 |
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