CN113004123A - 一种制备间苯三酚的方法 - Google Patents
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Abstract
Description
所属技术领域:
本发明涉及精细化学品制备领域,特别是涉及一种制备间苯三酚的方法
背景技术:
间苯三酚是重要的精细化工产品,主要用于药物合成的中间体,目前国内广泛以间苯三酚为原料制备黄酮、异黄酮等抗癌、抗心血管疾病类药物,作为平滑肌解痉药临床上用于治疗痉挛性疼痛。除了主要的医用价值之外,间苯三酚还可用作染料耦合剂,用于新型肽类燃料的合成,也可广泛用于轮胎增粘剂以及偶氮复合油墨等原料。间苯三酚世界年生产能力在500T以下,近几年来,由于新药合成的发展,其年需求量迅速增加,国外有关机构评估预计年需求量可达1000T左右,仅我国国内潜在年消耗将达300T,加之出口年需求量可达400T以上,且需求量仍在不断增加。
以2,4,6-三硝基甲苯(TNT)为原料,经氧化、还原和水解反应制得间苯三酚是工业化生产间苯三酚使用最广泛的反应路径。但是反应原料为炸药,有爆炸危险,反应过程中产生大量三废污染环境,对环境不友好,不符合可持续发展的战略方针。
2005年,Frost教授采用功能基团PhlD编辑到大肠杆菌中得到的工程菌发酵作为碳源的葡萄糖,在研究中发现合成乙酰基间苯三酚过程中得到了高纯度的间苯三酚,实现生物法单步骤制备间苯三酚。首次提出以六元环葡萄糖制备多元酚的路径。但是没有任何相关的后续研究报道,以糖为原料采用化学手段制备间苯三酚的研究更是空白。
纤维素是由葡萄糖为基本结构单元的大分子多糖,在酸性条件下可以水解生成葡聚糖,葡萄糖。葡萄糖的分子式是C6H12O6,而间苯三酚分子式为C6H6O3,理论上在不损失任何炭的前提下,脱三个水即可得到,符合原子经济性理念,是一条理想的绿色合成路径。鉴于前期研究,本发明首次提出以纤维素为原料,木质基炭为催化剂,采用催化法制备间苯三酚的路径。
发明内容:
本发明的目的在于提供一种制备间苯三酚的方法。
为了达到上述目的,本发明采用的技术方案包括:一种制备间苯三酚的方法,其特征在于:以林木废弃物树皮,秸秆等为原料,引入无机酸提供酸活性中心,水溶性金属盐提供Lewis酸活性中心,采用微波碳化法制备具有-Lewis双酸活性中心和微-介孔结构的双功能木质基炭催化剂,随后在水热降解条件下,以上述制备得到的催化剂催化纤维素定向制备间苯三酚,并实现催化剂的分离回收和循环使用。本发明首次提出以纤维素为原料,催化转化制备间苯三酚的工艺。
本发明的优点是:
1、以林木废弃物为催化剂原料,充分利用天然生物质,天然绿色环保。
2、首次提出以纤维素为原料制备间苯三酚的工艺,反应过程不脱碳,只脱水,复合原子经济性。
3、本发明改变了传统的生产工艺,采用绿色原料,催化工艺,反应过程操作简单,生产成本低,选择性高。
附图说明:
图1为本发明实施例1制备得到的催化剂的扫描图片;
图2为本发明实施例1纤维素降解产物质谱图;
图3为本发明实施例1产物间苯三酚质谱图。
具体实施方式:
下面对本发明实施作进一步详细描述:
一种制备间苯三酚的方法。其特征在于:以林木废弃物树皮,秸秆等为原料,引入无机酸提供酸活性中心,水溶性金属盐提供Lewis酸活性中心,采用微波碳化法制备具有-Lewis双酸活性中心和微-介孔结构的双功能木质基炭催化剂,随后在水热降解条件下,以上述制备得到的催化剂催化纤维素定向制备间苯三酚,并实现催化剂的分离回收和循环使用。本发明首次提出以纤维素为原料,催化转化制备间苯三酚的工艺。
下面,本发明将用实施例进行进一步的说明,但是它并不限于这些实施例的任一个或类似实例。
实施例1:
秸秆(40-80目)为原料,与磷酸质量比1:2浸渍混合,搅拌6小时后加入FeCl3溶液(秸秆质量:FeCl3=1:3)升温至90℃继续反应6小时,随后在105℃氛围下烘干12小时,冷却后,将得到的活化粉末放在微波反应器中,氮气氛围下600W,400℃反应10min。冷却后去离子水清洗后烘干,记为AC-1催化剂。通过吡啶红外和NH3-TPD测试,催化剂具有中强酸酸性,Lewis酸含量为86.2μmol/g,Bronsted酸含量为32.5μmol/g,介孔比表面积为265m2/g,微孔比表面积为153m2/g,证实AC-1为具有-Lewis双酸活性中心和微-介孔结构的双功能木质基炭催化剂。
取0.1g纤维素放入50mL不锈钢反应釜中,25mL水为溶剂,加入0.1g上述催化剂,反应条件:210℃,1MPa N2,1h,反应结束后将反应釜放在冷水浴中迅速冷却,过滤收集液体产物,0.22μm滤膜过滤后对产物进行气相色谱-质谱分析,纤维素转化率为98%,间苯三酚选择性达到49.6%。
实施例2:
树皮(40-80目)为原料,与稀硫酸质量比1:5浸渍混合,搅拌6小时后加入ZnCl2溶液(秸秆质量:ZnCl2=3:1)升温至110℃继续反应4小时,随后在105℃氛围下烘干12小时,冷却后,将得到的活化粉末放在微波反应器中,氮气氛围下700W,300℃反应20min。冷却后去离子水清洗后烘干,记为AC-2催化剂。通过吡啶红外和NH3-TPD测试,催化剂具有中强酸酸性,Lewis酸含量为93.1μmol/g,Bronsted酸含量为45.6μmol/g,介孔比表面积为295m2/g,微孔比表面积为131m2/g,证实AC-2为具有-Lewis双酸活性中心和微-介孔结构的双功能木质基炭催化剂。
取0.1g纤维素放入50mL不锈钢反应釜中,25mL水为溶剂,加入0.05g上述催化剂,反应条件:220℃,2MPa N2,0.5h,反应结束后将反应釜放在冷水浴中迅速冷却,过滤收集液体产物,0.22μm滤膜过滤后对产物进行气相色谱-质谱分析,纤维素转化率为100%,间苯三酚选择性达到51%。
Claims (8)
2.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:添加的无机酸可以使稀硫酸,磷酸,硝酸,盐酸中的一种或几种,原料与酸比例为2:1-6:1。
3.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:水溶性金属盐为FeCl3,偏铝酸钠,ZnCl2中的一种或几种,原料与金属盐的比例为5:1-1:5。
4.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:将上述混合物搅拌均匀后升温至60-150℃,反应1-10h。
5.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:得到的活化粉末放在微波反应器中,微波功率为400-1000W,反应温度为300-600℃,时间为5-60min。
6.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:制备催化剂的L酸含量为73.2-106.2μmol/g,B酸含量为29.1-61.5μmol/g,介孔比表面积为203-293m2/g,微孔比表面积为125-238m2/g。
7.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:上述催化剂催化纤维素反应,纤维素与催化剂比例为5:1-1:3,反应温度为180-250℃,反应压力为0.5-4MPa,反应时间为0.5-5h。
8.按照权利要求1所述的一种制备间苯三酚的方法,其特征在于:纤维素转化率为为96-100%,间苯三酚选择性为35-52%。
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