CN113333006A - 高分散钯/碳化钼催化剂及其在木质素衍生物选择性加氢脱氧制备烷基酚类中的应用 - Google Patents
高分散钯/碳化钼催化剂及其在木质素衍生物选择性加氢脱氧制备烷基酚类中的应用 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
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Abstract
本发明公开了一种高分散钯/碳化钼催化剂及其制备方法与其在木质素衍生物选择性加氢脱氧制备烷基酚类化合物中的应用,其是以钯盐和钼盐为原料,经混合、烘干、煅烧和程序升温碳化制备出所述高分散钯/碳化钼催化剂。该制备方法过程简单易实现,操作简便、安全,工艺参数易于控制,得到的钯/碳化钼催化剂中的活性金属钯以高分散的阳离子状态锚定在碳化钼表面与孔道内,使其可在温和条件下对木质素衍生物进行选择性加氢脱氧,并实现高活性、高选择性的丙基苯酚等烷基酚类物质的制备,且副产物少,有利于实行大规模生产。
Description
技术领域
本发明属于生物质能源科学与技术领域,具体涉及一种高效且可在温和条件下用于木质素衍生物选择性加氢脱氧制烷基酚类的高分散钯/碳化钼催化剂。
背景技术
酚类是工业上最重要的芳香族化学品之一,全球年产量为45万吨,主要用作合成聚合物前体、非离子表面活性剂、农药、润滑剂添加剂、除草剂和药物。酚类主要由石油衍生的苯生产,早期主要从煤焦油中的粗酚精制获得。随着其需求量的不断提高,出现了磺化碱熔法、异丙苯法和甲苯氯化法等生产方法。其中,磺化碱熔法是用浓硫酸或三氧化硫作为磺化剂,使苯进行气相磺化后用亚硫酸钠中和,再与熔融状态的烧碱作用生成苯酚钠及溶解于水的Na2SO3并结晶分离,分离后的苯酚钠溶液用二氧化硫或稀硫酸酸化而制得粗品,经减压蒸馏而得成品。该方法消耗大量硫酸等强酸和烧碱等强碱,对环境污染较大,同时能耗较高,在当前节能减排的发展趋势下已被逐步淘汰。异丙苯法是用丙烯在三氯化铝催化剂催化下,于80~90℃、常压条件下和苯进行烃化反应,经蒸馏分离得到异丙苯,将异丙苯用空气在100~120℃、300~400 kPa压力下直接氧化成过氧化氢异丙苯,过氧化氢异丙苯用硫酸在60℃常压下裂解为苯酚和丙酮,最后经精制分别得丙酮和苯酚。该方法成本低廉,且三废较少,适用于大型化连续化生产,目前世界上苯酚的生产大都采用该方法,但其原料主要来自于不可再生的石油资源,且工业生产过程的中间产物苯属于强致癌物,依然具有潜在的环境保护风险。
能源紧张与环境保护是当前人类社会面临的共同挑战。化石资源作为不可再生资源,每年消耗量巨大,而木质素纤维素生物质资源年生产量达到1700亿吨,由甲氧基苯丙烷单元构成的木质素在理论上可以替代化石资源制备大宗化学品如烯烃,芳香烃等。开发和利用此类“阳光资源”,有望解决化石资源短缺的问题。
木质素中富含芳醚结构,具有丰富的芳醚键,这些芳醚结构键能较高,常规热催化手段难以脱除,所以,采用可以高效活化醚键同时不会破坏酚羟基的催化剂进行选择性加氢脱氧是一种很有前景的木质素提质手段。然而,要获得单一高收率产物是一个巨大的挑战,因为木质素及其衍生物通常具有多个酚羟基和芳醚基团,加氢脱氧过程往往难以精确控制反应程度,得到的产物往往是苯类、芳醚类和酚类的混合物。常用的木质素及其衍生物选择性加氢脱氧催化剂,如5%Pd/C催化剂,在以F5H转基因杨木屑作为底物的反应中,单体得率约为76.7%,且为4种单体的混合物(Science, 2016, 354, 329-333)。以木质素衍生物丁香酚做为底物的反应中,以Au/Nb2O5作为催化剂,烷基酚类的得率约为84.2%,但其反应时所需的初始氢气压力为6 MPa,过高的初始压力大大限制了其工业化应用的可能(GreenChem., 2019, 21, 3081-3090)。
碳化钼具有较高的比表面积,对酚羟基具有较强的吸附能力,可以有效地吸附木质素结构中的酚羟基,提高产物的转化率与选择性。另外,贵金属等是高效的加氢催化剂,将其负载在过渡金属碳化物上进行一系列催化反应如水煤气反应、脱硫反应等一直是科学研究的热点内容。但贵金属用量大会造成催化剂成本比较高,且活性组分钯的纳米颗粒分散于所述载体的表面或孔口,易造成金属流失。因此,降低贵金属的负载量,制备在温和条件下对木质素及其衍生物高效选择性加氢脱氧制备烷基酚类且活性稳定的高分散钯/碳化钼催化剂,对于木质素的高效提质利用十分重要。
发明内容
本发明的目的在于提供一种高分散钯/碳化钼催化剂及其制备方法与在温和条件下实现木质素衍生物的选择性加氢脱氧制备烷基酚类过程中的应用。其制备工艺简便,原子利用率高,对木质素模型分子如愈创木酚、丁香酚等选择性加氢脱氧制备烷基酚类的反应具有高活性、高选择性的特点,为木质素衍生物高效转化为高附加值化学品提供了新的途径。
为实现上述目的,本发明采用如下技术方案:
一种高分散钯/碳化钼催化剂,其中钯以高分散的阳离子状态锚定在多孔碳化钼表面及孔道内;钯和钼的原子比为0.01-5%。高分散状态的贵金属催化活性高,能够有效降低贵金属的负载量,碳化钼载体对酚羟基的特殊吸附形式抑制了复杂的副反应。
所述高分散钯/碳化钼催化剂的制备方法,是将钯盐和钼盐分别加水溶解,然后在搅拌条件下将钯盐溶液滴加入钼盐溶液中,滴加完毕后继续搅拌2-5小时,随后升温至80℃,继续搅拌至溶液蒸干;将得到的固体产物经60-120℃干燥后,于300-600℃煅烧1-6h,然后在还原性气体条件下进行程序升温碳化,获得所述高分散钯/碳化钼催化剂。
其中,所述钯盐为硝酸钯、氯钯酸铵中的任意一种;所述钼盐为钼酸铵、四钼酸铵、七钼酸铵中的任意一种。
所用还原性气体为甲烷和氢气的混合气体,其中甲烷与氢气体积比为10%-50%,气体总流量为20-100ml/min。
所述程序升温碳化的初始温度为30℃-50℃,终点温度为600℃-900℃,升温速度为1-10℃/min,保温时间为30-240分钟。
本发明所得高分散钯/碳化钼催化剂可用于温和条件下木质素衍生物的选择性加氢脱氧制备烷基酚类化合物。其应用步骤为:将高分散钯/碳化钼催化剂和木质素衍生物(如愈创木酚、二氢丁香酚等)置于反应器中,再加入有机溶剂,密封反应器后充入0.1-2MPa的H2,设定反应温度为180-300℃,反应时间为0.5-24 h。反应结束后,将反应器置于冰浴中迅速冷却。
在所述木质素衍生物的选择性加氢脱氧反应中,所用氢气压力较低,烷基酚类产物的得率通常在90%以上,且催化剂循环多次后活性不变等。
本发明的有益效果在于:
(1)本发明以钯盐和钼盐为原料,通过混合、烘干、煅烧和程序升温碳化制备出高分散钯/碳化钼催化剂,其中,活性金属钯以高分散的阳离子状态锚定在碳化钼表面和孔道内,能有效减少贵金属的使用量。
(2)本发明制备过程简单易实现,操作简便、安全,工艺参数易于控制,得到的高分散钯/碳化钼催化剂应用于木质素衍生物如愈创木酚、二氢丁香酚等的选择性加氢脱氧制备烷基酚类的反应中,可表现出高活性、高选择性及良好的稳定性,其烷基酚类总选择性大于95%,且催化剂多次循环后活性不变,适用于大规模生产,在木质素转化领域具有良好的应用前景。
附图说明
图1为实施例1制备的Pd/MoC催化剂的透射电镜图和元素分布图。
图2为实施例1所制备的Pd/MoC催化剂在选择性加氢脱氧反应前、后的XRD对比图。
图3为实施例1制备的Pd/MoC催化剂进行选择性加氢脱氧循环反应的稳定性测试情况。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
将2g (NH4)6Mo7O24溶解在10 mL去离子水中,并在室温下充分搅拌20分钟。在超声处理条件下,将0.0052g Pd(NO3)2溶解在5 mL去离子水中,然后将其缓慢注入上述(NH4)6Mo7O24水溶液中。将混合物溶液在室温下搅拌4小时,然后升温至80℃并继续搅拌直至水完全干燥。将获得的固体在真空条件下80℃干燥过夜,然后以5℃/ min的速率升温至500℃煅烧4 h,最后在管式炉中、还原性气体条件下以程序升温的方式进行碳化;其升温程序为:初始温度:30℃,以5℃/ min的速度升至700℃,并保持120分钟;所述还原性气体中H2/CH4的体积比为4:1,总气体流量为60 mL / min。程序升温碳化后得到黑色固体,即为0.2 at %的钯/碳化钼催化剂,记为0.2-Pd/MoC。
将实施例1所制备的钯/碳化钼催化剂进行透射电镜表征与元素分布分析,结果见图1。由钯/碳化钼催化剂的透射电镜图只观察到碳化钼载体,而并没有在其表面观察到任何Pd颗粒和PdO颗粒,这与XRD结果一致。由钯/碳化钼催化剂的高角环暗场图以及Pd和Mo的元素分布图中可以清晰地观察到,钯/碳化钼催化剂存在两系列高分散的Pd和Mo活性位点。
应用实施例1
在实施例1所述制备方法的基础上通过改变钯盐的加入量,以分别制备Pd负载量为1 at%和5 at%的两种Pd/MoC催化剂,分别记为1-Pd/MoC和5-Pd/MoC。然后将0.2-Pd/MoC和制备的催化剂1-Pd/MoC、5-Pd/MoC分别取100mg,与3 mmol底物、9.5g溶剂一同加入25 ml石英内胆中,装入高压反应釜。高压反应釜密封完全后,用氢气清洗釜腔去除空气后通入一定量氢气,升温反应后立即将釜体进行冰水浴降温。为了准确计算转化速率,控制转化率低于80%,反应温度设为250℃,反应时间设为1小时,氢气压力为0.5 MPa,结果如表1所示。
表1 不同催化剂对木质素衍生物愈创木酚的催化效果对比
由表1可见,本发明所得Pd/MoC催化剂中Pd负载量对木质素衍生物的选择性加氢脱氧反应有较大影响,0.2 at%是最优负载量。
应用实施例2
将100 mg实施例1制备的钯/碳化钼催化剂与15 ml甲醛稳定酸解木质素/二氧六环溶液一同加入25 ml石英内胆中,装入高压反应釜。高压反应釜密封完全后,用氢气清洗釜腔去除空气后通入2 MPa氢气,升温至280℃反应15小时,反应完成后立即将釜体进行冰水浴降温。
将实施例1所制备的钯/碳化钼催化剂在反应前、后进行XRD表征,结果见图2。图中只呈现了碳化钼的衍射峰,而并没有观察到Pd以及PdO颗粒的衍射峰,说明制备的钯/碳化钼催化剂并没有形成Pd颗粒和PdO颗粒,且其反应后结构也没有发生明显变化。
将实施例1制备的催化剂进行选择性加氢脱氧循环实验测试其稳定性,结果见图3。从图中可以看出,在循环使用四次后,钯/碳化钼催化剂依然具有和新鲜催化剂相近的催化活性。
对比例
采用湿法浸渍分别制备Pd/Mo/Al2O3、Pd/Mo/TiO2和Pd/MoO3三种对比催化剂,其中Pd负载量为0.2 wt%,Pd/Mo/Al2O3和Pd/Mo/TiO2中Mo负载量为0.5 wt%。然后将实施例1和对比例制备的催化剂分别取100mg,与3mmol底物、9.5g溶剂一同加入25 ml石英内胆中,装入高压反应釜。高压反应釜密封完全后,用氢气清洗釜腔去除空气后通入一定量氢气,升温反应后立即将釜体进行冰水浴降温。为了准确计算转化速率,控制转化率低于80%,反应温度设为260oC,反应时间设为1.5小时,氢气压力为0.5 MPa,结果如表2所示。
表2 不同催化剂对木质素衍生物二氢丁香酚的催化效果对比
由表2可见,本发明所得Pd/MoC催化剂对木质素衍生物二氢丁香酚的选择性加氢脱氧反应具有良好的转化率和选择性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (9)
1.一种高分散钯/碳化钼催化剂,其特征在于,所述催化剂中钯以高分散的阳离子状态锚定在多孔碳化钼表面及孔道内;钯和钼的原子比为0.01-5%。
2.一种如权利要求1所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,将钯盐和钼盐分别加水溶解,然后在搅拌条件下将钯盐溶液滴加入钼盐溶液中,滴加完毕后继续搅拌2-5小时,随后升温至80℃,继续搅拌至溶液蒸干;将得到的固体产物经干燥、煅烧后,在还原性气体条件下进行程序升温碳化,获得所述高分散钯/碳化钼催化剂。
3.根据权利要求2所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,所述钯盐为硝酸钯、氯钯酸铵中的任意一种;所述钼盐为钼酸铵、四钼酸铵、七钼酸铵中的任意一种。
4.根据权利要求2所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,所述干燥的温度为60-120℃。
5.根据权利要求2所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,所述煅烧的温度为300-600℃,时间为1-6h。
6. 根据权利要求2所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,所用还原性气体为甲烷和氢气的混合气体,其中甲烷与氢气体积比为10%-50%,气体总流量为20-100ml/min。
7.根据权利要求2所述的高分散钯/碳化钼催化剂的制备方法,其特征在于,所述程序升温碳化的初始温度为30℃-50℃,终点温度为600℃-900℃,升温速度为1-10℃/min,保温时间为30-240分钟。
8.一种如权利要求1所述的高分散钯/碳化钼催化剂对木质素衍生物进行选择性加氢脱氧制备烷基酚类化合物中的应用。
9.根据权利要求8所述的应用,其特征在于:所述木质素衍生物包括愈创木酚或二氢丁香酚。
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