CN110003010A - 一种直接利用木糖制备乙酰丙酸酯的方法 - Google Patents
一种直接利用木糖制备乙酰丙酸酯的方法 Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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Abstract
本发明公开一种直接利用木糖制备乙酰丙酸酯的方法,属于生物质能源化工的技术领域。本发明所述方法以木糖为反应起始原料,以低级烷醇为反应介质,负载型分子筛Zr/MCM‑41和杂多酸的混合体系为催化剂,在140~150℃下反应10~14h,最高可直接获到53.0%收率的乙酰丙酸酯产物;该转化利用途径所用催化剂体系廉价易得、并易分离回收重复使用;一步合成反应过程简单,经济高效,能耗低;反应条件温和,不需要外加氢气,安全环保;目标产物收率和利用附加值高,具备良好的工业应用前景。
Description
技术领域
本发明涉及一种直接利用木糖制备乙酰丙酸酯的方法,属于生物质能源化工的技术领域。
背景技术
木糖又称五碳醛糖,是一种戊糖,以大分子木聚糖的形式广泛存在于植物半纤维素中,可由玉米芯、甘蔗渣、秸秆等农林固体废弃生物质在酸性介质中降解制得。木糖具有广泛的工业应用价值,如可在食品、饮料中作为无热量甜味剂;另外,木糖也可以转化为糠醛、糠醇、木糖醇等重要的工业化工产品。基于目前国内外对生物质精炼模式的日益重视,进一步开发基于木糖的高值化、能源化新产品和新技术具有重要的现实和战略意义,它们的大规模利用将有助于解决石化资源短缺及其应用带来的环境问题,从而实现可持续发展。
乙酰丙酸酯是一类重要的化学中间体和新能源化学品,具有高的反应特性和广泛的工业应用价值;它的分子中含有羰基和酯基,具有良好的化学反应活性,可发生水解、酯交换、加成、取代、氧化还原等有机反应,作为反应底物可获取多种具有工业意义的化工产品。同时,乙酰丙酸酯也可以作为运输燃料的汽油和柴油添加剂,并且在低温条件下能保持较好的稳定性和流动性能,是优良的生物基新型燃料;此外在香精香料行业也有广泛的应用。研究表明从生物质基木糖出发可以获取乙酰丙酸酯,但需经历多个反应过程。首先木糖需经酸催化转化生成糠醛;然后糠醛经加氢还原反应生成糠醇;最后糠醇在酸催化作用下醇解可获得乙酰丙酸酯。以上每步反应过程目前均有研究报道并可实现有效转化,但以木糖为起始原料到最终获得乙酰丙酸酯所需反应步骤多、工艺复杂,整个过程所用能耗高,同时由于涉及到高压加氢反应,对反应设备要求高。因此,尽管各步反应过程均能有效地进行,但从整个工艺过程计算最终乙酰丙酸酯收率并不高、经济性差,不适合工业化生产。
发明内容
本发明的目的在于提供一种生物质基木糖直接制备乙酰丙酸酯的方法,该方法中使用的催化剂成本低廉易得,易回收分离,同时能在温和条件下反应,具体步骤为:按负载型分子筛和杂多酸的质量比为1:1~2:1的比例取负载型分子筛和杂多酸加入到反应釜中得到混合物A,然后加入由低级烷醇和木糖混合得到的混合物B,在140~150℃下反应10h~14h,即可得目标产物乙酰丙酸酯,其中混合物B中木糖浓度为5~10g/L;混合物A与混合物B的质量体积比为0.15 g ~0.2g:10mL。
优选的,本发明所述负载型分子筛为Zr/MCM-41。
优选的,本发明所述Zr/MCM-41制备方法为:将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41,连续搅拌18~24h,减压蒸馏至水分完全蒸发,干燥、焙烧后即可制得负载型分子筛Zr/MCM-41,其中Zr(NO3)4•5H2O与MCM-41的质量比为0.57~0.85:1;干燥的条件为105℃下干燥12h,焙烧的条件为500~550℃下焙烧3h。
优选的,本发明所述杂多酸为硅钨酸或者磷钨酸,市场直接购买。
优选的,本发明所述低级烷醇为异丙醇或者仲丁醇,市场直接购买。
本发明的原理:在本发明所述催化体系中,木糖和低级烷醇合成乙酰丙酸酯的反应路径如下:(1)木糖首先在布朗斯特酸杂多酸的催化作用下脱水生成糠醛;(2)糠醛在Zr/MCM-41的催化作用下与低级烷醇发生催化转移加氢反应生成糠醇;(3)生成的糠醇进一步在布朗斯特酸杂多酸作用下醇解生成乙酰丙酸酯;该三步反应是一个连续的串联反应,在同一反应器中实现一锅转化。
本发明的有益效果为:
(1)本发明通过催化剂和反应介质体系进行多级过程调控,实现直接从木糖出发一锅制备乙酰丙酸酯的过程反应,该转化利用途径一步合成反应过程简单,经济高效,能耗低,简化了反应设备。
(2)直接使用木糖作为反应原料,来源丰富,原料成本低,所用催化剂体系廉价易得、无贵金属使用,并易分离回收重复使用。
(3)采用低级烷醇作为溶剂和反应介质的同时,还可作为氢转移源实现反应过程中的加氢还原反应,不需要外加高压氢气,从而达到节能安全环保的目的,所得目标产物乙酰丙酸酯收率较高,具备良好的工业应用前景。
(4)反应条件温和,不需要外加氢气,安全环保,产物乙酰丙酸酯得率最高可达到53.0%,具有良好工业应用前景。
具体实施方式
下面结合实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌18h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在530℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g硅钨酸加入到反应釜中(Zr/MCM-41和硅钨酸的用量均为10g/L),然后加入10mL仲丁醇和0.1g木糖的混合物(混合物中木糖浓度为10g/L),在150℃下反应10h,即得制得乙酰丙酸仲丁酯;用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为38.7%。
实施例2
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在550℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量均为10g/L),然后加入10mL仲丁醇和0.08g木糖的混合物(混合物中木糖浓度为8g/L),在150℃下反应10h,即得制得乙酰丙酸仲丁酯。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为46.4%。
实施例3
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.85:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在550℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量均为10g/L),然后加入10mL仲丁醇和0.08g木糖的混合物(混合物中木糖浓度为8g/L),在150℃下反应10h,即得制得乙酰丙酸仲丁酯。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为47.3%。
实施例4
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在500℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量均为10g/L),然后加入10mL仲丁醇和0.05g木糖的混合物(混合物中木糖浓度为5g/L),在150℃下反应10h,即得制得乙酰丙酸仲丁酯。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为43.2%。
实施例5
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在550℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.05g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量分别为10g/L和5g/L),然后加入10mL仲丁醇和0.05g木糖的混合物(混合物中木糖浓度为5g/L),在150℃下反应12h,即得制得乙酰丙酸仲丁酯。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为53.0%。
实施例6
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在550℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量均为10g/L),然后加入10mL仲丁醇和0.05g木糖的混合物(混合物中木糖浓度为5g/L),在140℃下反应14h,即得制得乙酰丙酸仲丁酯。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为43.4%。
实施例7
(1)将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41(Zr(NO3)4•5H2O与载体MCM-41的质量比为0.57:1),连续搅拌24h后,减压蒸馏至水分完全蒸发;然后在105℃下干燥12h,最后在550℃下焙烧3h,制得Zr/MCM-41负载型分子筛。
(2)取0.1g负载型分子筛Zr/MCM-41和0.1g磷钨酸加入到反应釜中(Zr/MCM-41和磷钨酸的用量均为10g/L),然后加入10mL异丙醇和0.05g木糖的混合物(混合物中木糖浓度为5g/L),在145℃下反应12h,即得制得乙酰丙酸异丙酯;用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸异丙酯得率为37.4%。
实施例8
催化剂回收实验:对实施例2中使用后的负载型分子筛Zr/MCM-41和磷钨酸进行分离回收,并将Zr/MCM-41在550℃下焙烧3h进行再生,按实施例2条件进行重复利用实验。用液相色谱和气相色谱分析,木糖转化率为100%,乙酰丙酸仲丁酯得率为52.3%。
Claims (6)
1.一种直接利用木糖制备乙酰丙酸酯的方法,其特征在于:按负载型分子筛和杂多酸的质量比为1:1~2:1的比例取负载型分子筛和杂多酸加入到反应釜中得到混合物A,然后加入由低级烷醇和木糖混合得到的混合物B,在140~150℃下反应10h~14h,即可得目标产物乙酰丙酸酯,其中混合物B中木糖浓度为5~10g/L;混合物A与混合物B的质量体积比为0.15 g~0.2g:10mL。
2.根据权利要求1所述直接利用木糖制备乙酰丙酸酯的方法,其特征在于:所述负载型分子筛为Zr/MCM-41。
3.根据权利要求2所述直接利用木糖制备乙酰丙酸酯的方法,其特征在于:Zr/MCM-41制备方法为:将Zr(NO3)4•5H2O溶解在去离子水中,然后加入载体MCM-41,连续搅拌18~24h,减压蒸馏至水分完全蒸发,干燥、焙烧后即可制得负载型分子筛Zr/MCM-41,其中Zr(NO3)4•5H2O与MCM-41的质量比为0.57~0.85:1。
4.根据权利要求3所述直接利用木糖制备乙酰丙酸酯的方法,其特征在于:干燥的条件为105℃下干燥12h,焙烧的条件为500~550℃下焙烧3h。
5.根据权利要求1所述直接利用木糖制备乙酰丙酸酯的方法,其特征在于:杂多酸为硅钨酸或者磷钨酸。
6.根据权利要求1所述直接利用木糖制备乙酰丙酸酯的方法,其特征在于:低级烷醇为异丙醇或者仲丁醇。
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