CN115043708A - 一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法 - Google Patents
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法 Download PDFInfo
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Abstract
本发明公开一种在氢气还原氛围中以γ‑丁内酯作溶剂的条件下催化顺丁烯二酸酐加氢合成1,4‑丁二醇的方法。本发明首先采用一种纳米乳液诱导自组装的方法制备具有高比表面积和多级孔结构的氮掺杂碳纳米微球(HPNC),再将Ru超细纳米颗粒高分散锚定在HPNC上即制得Ru/HPNC催化剂;然后,将Ru/HPNC催化剂、顺丁烯二酸酐、溶剂γ‑丁内酯加入高压反应釜中,充入0.5‑2.5MPa H2,50‑150℃下反应2‑5h,即可催化顺丁烯二酸酐加氢合成1,4‑丁二醇,1,4‑丁二醇的收率高达99%。本发明的方法中,Ru/HPNC催化剂制备方法简单,活性位点为高分散负载的超细Ru纳米颗粒;采用催化加氢、以γ‑丁内酯作溶剂的催化体系合成1,4‑丁二醇的方法简单、绿色、产物易于分离,且1,4‑丁二醇的收率高,易于工业化生产。
Description
技术领域
本发明涉及一种精细化学品1,4-丁二醇的制备方法,确切地讲是一种以顺丁烯二酸酐为原料,以Ru/HPNC为催化剂,在γ-丁内酯作溶剂的反应条件下经催化加氢合成1,4-丁二醇的方法。
背景技术
1,4-丁二醇是一种重要的化工原料,主要用于生产聚四亚甲基二醇醚、聚对苯二甲酸丁二醇酯、聚氨酯、聚丁二酸丁二醇酯等。它被广泛用于制药、化工、纺织、造纸、汽车和日用化学品等领域。工业生产中对1,4-丁二醇的需求量很大,由于近年来国家禁塑令的颁布,1,4-丁二醇作为可降解塑料聚丁二酸丁二醇酯的重要原料,其需求量大大增加,采用环境友好和经济的方法大批量合成1,4-丁二醇具有重要意义。
目前,工业化生产1,4-丁二醇的方法有4种,分别为:炔醛法、顺酐法、烯丙醇法、丁二烯法和环氧丙烷法。传统炔醛法由于其设备造价高、操作条件苛刻、压力高、原料乙炔远程储运有危险,以及廉价乙炔的获得量很有限等原因,目前建厂很少采用此技术。改良炔醛法改进了操作条件,使操作压力降低,生产的安全性得到了提高,同时降低了投资,适合于大规模工业化生产,提高了炔醛法的竞争力,它也是目前1,4-丁二醇生产所选择的主要技术之一,但同样存在着原料乙炔远程储运有危险以及廉价乙炔的获得量很有限等缺点。除炔醛法工艺技术外,烯丙醇法、丁二烯法的原料全部来自于石油路线,在大型炼油石化企业能够得到廉价的原料来源利用这两种技术建设1,4-丁二醇装置,生产的1,4-丁二醇产品尚有市场竞争力,如果依靠购买高价的石油化工产品丁二烯、环氧丙烷做原料生产1,4-丁二醇,在石油价格不断升高的情况下,很难和采用炔醛法工艺技术生产的1,4-丁二醇产品相竞争。同时,也有较多的废水排放,会对环境造成一定的污染。
随着化学工业的不断发展,人们对环境的重视程度越来越高,环境保护和污染治理的力度也越来越大。单纯的污染物处理不能满足可持续发展的要求,从源头上控制、减少甚至消除污染成为化工行业必须面对的问题,绿色催化开始成为化工生产持续健康发展的趋势。因此,有必要按照绿色化学的理念,设计和开发一种具有较高经济效益的催化顺丁烯二酸酐合成1,4-丁二醇的催化加氢工艺。目前,已报道的1,4-丁二醇生产方法仍有许多不容忽视的问题,专利EP1997310014(Improved catalysts for the hydrogenation ofmaleic acid to 1,4-butanediol)公开了使用由负载在碳载体上的钯和铼组成的加氢催化剂催化羧酸、内酯或酸酐加氢;专利US10110444(Process for the simultaneousproduction of maleic anhydride and its hydrogenated derivatives)公开了一种同时生产顺丁烯二酸酐及其加氢衍生物如1,4-丁二醇的方法;专利JP2670698B2(1,4-ブタンジオールの製法)通过使用特定的固体催化剂在气相中对顺丁烯二酸酐进行催化加氢,在低压下一步简化生产工艺;在含有Cu和Mn的固体催化剂存在下,在γ-丁内酯等溶剂中,在170-280℃、10-100kg/cm2的压力和1,000-100,000hr-1的气相条件下,用H2催化加氢,进行后续生产;专利CN94108094.3(1,4-丁二醇的制备方法)公开了以顺酐为原料,在特定的催化剂存在下进行气相催化加氢反应制备1,4-丁二醇;但上述方法在制备1,4-丁二醇过程中均存在1,4-丁二醇收率低和选择性不高的问题。专利CN101307042A报道以CuO为活性组分添加载体和助剂制备加氢催化剂,专利CN1493569A中公开的CuO-MnO2-Al2O3催化剂,专利EP0143634中公开的CuO-Cr2O3催化剂,专利CN1182732A中公开的CuO-Cr2O3-Al2O3催化剂,专利WO82/03854中公开的CuO-ZnO催化剂,以及专利EP0373947报道的CuO-Cr2O3-MnO2催化剂等,这些催化剂都在加氢反应中有较好的活性,但脱水的能力比较弱。在众多报道的催化剂中,钌基催化剂被认为是催化转化顺丁烯二酸酐的最有前途的催化剂之一。与其它非贵金属如铜、镍和钴相比,钌具有更好的活性和稳定性;与其它铂基贵金属相比,它在顺酐的催化转化中具有更高的活性和选择性,同时它也是最便宜的贵金属之一。因此,精确设计具有稳定活性和较高原子利用率的超细钌纳米颗粒负载型催化剂对顺丁烯二酸酐的催化加氢制备1,4-丁二醇具有重要意义。
发明内容
本发明的目的是:提供一种更加经济高效,符合绿色环保要求,以γ-丁内酯作溶剂的催化加氢策略合成1,4-丁二醇的方法(如下式所示)。本发明的另一目的是提供上述催化加氢方法中Ru/HPNC催化剂的制备方法。
为解决本发明的技术问题采用如下技术方案:
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将一定量的Ru/HPNC催化剂、顺丁烯二酸酐和γ-丁内酯加入高压反应釜中,向高压反应釜中充入一定压力的氢气,程序升温到一定温度后反应一定时间,并用气相色谱仪实时监测分析顺丁烯二酸酐的转化率、1,4-丁二醇的收率。
所述催化加氢反应在高压反应釜中进行。
所述氢气压力为0.5-2.5MPa。
所述反应温度为50-150℃,反应时间2-5小时。
所述催化加氢方法中使用的Ru/HPNC催化剂,具体制备方法如下:首先以盐酸多巴胺为氮源和碳源,通过纳米乳液诱导自组装的方法制备具有高比表面积和多级孔结构的氮掺杂碳纳米微球(HPNC);然后,以HPNC为载体,通过浸渍法、还原法制备Ru/HPNC催化剂,即首先将一定量的催化剂载体HPNC通过超声均匀分散在丙酮溶液中,再将按一定质量配比配制的十二羰基合钌的丙酮溶液滴加到上述混合物中,充分吸附浸渍,浸渍后的样品通过旋转蒸发去除溶剂,得到的固体再置于管式炉中程序升温至200-400℃,在氢气还原气氛中焙烧2小时,即得到Ru/HPNC催化剂。
所述制备的Ru/HPNC催化剂中金属与载体的质量比为Ru:HPNC=0.005-0.03:1。
所述催化剂制备方法中,还原气氛为VH2:VAr=1:9,还原气流量为20mL/min,升温速率为2-10℃/min。
本发明的优点:1.本发明设计和制备的Ru/HPNC催化剂主要采用简单的自组装法、浸渍法和焙烧还原法制备,工艺简单、温和、成本低。2.以马来酸酐为原料,γ-丁内酯为溶剂,氢气为还原剂,在高压催化加氢的条件下合成1,4-丁二醇;超细Ru纳米颗粒均匀分散的活性位点使反应在较温和的条件下高效合成1,4-丁二醇,使用γ-丁内酯作为反应溶剂大大提高了产品的转化率,减少了副产品的产生,并省去了分离副产品的步骤。3.本发明提供的催化加氢合成1,4-丁二醇的方法采用"一锅法",操作方法简单,易于控制,有利于工业应用和规模化生产。
附图说明
图1为本发明实施例1制备的HPNC载体的透射电镜图。
图2为本发明实施例1制备的Ru/HPNC催化剂的透射电镜图。
具体实施方式
实施例1
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将1g聚氧乙烯聚氧丙烯醚嵌段共聚物F127和0.5g多巴胺溶解在100mL水和乙醇混合物(体积比1:1)中,并将2mL均三甲苯缓慢注入上述溶液中,形成纳米乳液体系。连续搅拌30min后,在室温下,将5.0mL氨水滴入上述混合液中,诱导多巴胺自聚12h。然后过滤,将所得的黑色固体以1℃/min升温至800℃,氩气气氛下焙烧2h,即制得HPNC载体。再将150mg HPNC和5-30mg的(CO)12Ru3加入含有40mL丙酮的烧瓶中,将混合物超声分散30min,并在室温下搅拌4小时后,通过旋转蒸发去除溶剂,所得固体经干燥后置于管式炉中在H2/Ar氛围下,200℃-400℃焙烧还原2小时即制得Ru/HPNC催化剂,催化剂中Ru含量为0.5%-3%。
实施例2
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将6.5g顺丁烯二酸酐固体、10mLγ-丁内酯加入100mL的高压反应釜中,然后加入实施例1中的Ru(0.5%)/HPNC催化剂100mg,充入1.5MPa的H2,90℃下反应3h,用气质联用仪分析检测,顺丁烯二酸酐转化率为61%,1,4-丁二醇的选择性为87%。
实施例3
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将6.5g顺丁烯二酸酐固体、10mLγ-丁内酯加入100mL的高压反应釜中,然后加入实施例1中的Ru(1.5%)/HPNC催化剂100mg,充入2MPa的H2,90℃下反应3h,用气质联用仪分析检测,顺丁烯二酸酐转化率为89%,1,4-丁二醇的选择性为95%。
实施例4
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将6.5g顺丁烯二酸酐固体、10mLγ-丁内酯加入100mL的高压反应釜中,然后加入实施例1中的Ru(2.0%)/HPNC催化剂100mg,充入2.5MPa的H2,100℃下反应3h,用气质联用仪分析检测,顺丁烯二酸酐转化率为97%,1,4-丁二醇的选择性为96%。
实施例5
一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,具体方法如下:将6.5g顺丁烯二酸酐固体、10mLγ-丁内酯加入100mL的高压反应釜中,然后加入实施例1中的Ru(3.0%)/HPNC催化剂100mg,充入2.5MPa的H2,100℃下反应3h,用气质联用仪分析检测,顺丁烯二酸酐转化率为100%,1,4-丁二醇的选择性为99%。
Claims (7)
1.一种顺丁烯二酐酸催化加氢合成1,4-丁二醇的方法,其特征在于:首先,以盐酸多巴胺、聚氧乙烯聚氧丙烯醚嵌段共聚物F127为原料,通过纳米乳液诱导自组装并高温热解的方法制备具有高比表面积和多级孔结构的氮掺杂碳纳米微球(HPNC);接着,将HPNC浸渍于按一定质量配比配制的十二羰基合钌的丙酮溶液中,充分吸附浸渍后,固体样品通过旋转蒸发去除溶剂,再置于管式炉中程序升温至200-400℃,在氢气还原气氛中焙烧2-5小时,即得到Ru/HPNC催化剂;将顺丁烯二酸酐、γ-丁内酯、Ru/HPNC催化剂加入高压反应釜中,充入高压H2,90℃下反应3h,催化顺丁烯二酸酐加氢合成1,4-丁二醇。
2.根据权利要求1所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:催化剂为超细Ru纳米颗粒高分散均匀负载的氮掺杂碳纳米微球催化剂,Ru纳米颗粒的平均粒径为3nm。
3.根据权利要求1所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:Ru/HPNC催化剂制备方法中,还原气氛为VH2:VAr=1:9,还原气流量为25mL/min,升温速率为2-10℃/min。
4.根据权利要求1所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:Ru/HPNC催化剂中金属与载体的质量比为Ru:HPNC=0.005-0.03:1。
5.根据权利要求1所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:顺丁烯二酸酐催化加氢合成1,4-丁二醇的反应氢气压力为0.5-2.5MPa,反应温度为50-150℃。
6.根据权利要求1和5所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:反应在以γ-丁内酯作溶剂的条件下进行。
7.根据权利要求1和5所述的一种顺丁烯二酸酐催化加氢合成1,4-丁二醇的方法,其特征在于:利用气相色谱或气质联用仪分析检测反应效果,顺丁烯二酸酐转化率高于98%,1,4-丁二醇的选择性高于99%。
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