CN108607553A - 一种甘油氢解制备1,3-丙二醇的催化剂及制备和应用 - Google Patents
一种甘油氢解制备1,3-丙二醇的催化剂及制备和应用 Download PDFInfo
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Abstract
该专利涉及一种甘油氢解制备1,3‑丙二醇的催化剂及其制备方法,催化剂由Nb、Ta等过渡金属掺杂的氧化钨载体负载活性组分Pt,Pd或助剂金属构成。催化剂的制备方法包括:a)水热法或溶剂热法制备催化剂载体Nb、Ta等过渡金属掺杂的氧化钨;b)用Pt,Pd或助剂金属的前驱体溶液浸渍催化剂载体并烘干还原,得到Pt,Pd或助剂金属/过渡金属掺杂型氧化钨催化剂。该专利所制得的催化剂,可以使甘油水溶液在较大的氢气压力范围和较大的温度范围内高选择性地氢解生成1,3‑丙二醇。
Description
本发明涉及一种甘油氢解制备1,3-丙二醇的催化剂;具体为采用水热或溶剂热方法制备过渡金属掺杂的氧化钨载体,采用浸渍法担载活性贵金属组分,获得高分散的贵金属担载催化剂。
技术背景
随着生物柴油的飞速发展,生产生物柴油过程中的副产物甘油大量过剩,转化甘油制备高价值化学品成为提升生物柴油产业经济性的有效手段。甘油可以通过氢解反应生成1,3-丙二醇、1,2-丙二醇等,其中1,3-丙二醇是生产聚对苯二甲酸丙二醇酯(PTT)的重要单体。PTT是一种具有生物可降解性的新型聚酯纤维,它克服了聚对苯二甲酸乙二醇酯(PET)太硬和聚对苯二甲酸丁二醇酯(PBT)太软的缺点,同时具有优异的回弹性,易染性,生物降解性等,在地毯、纺织工程塑料等行业具有巨大的发展潜力。
目前1,3-丙二醇的工业生产方法有Shell公司的环氧乙烷羰基化加氢法和Degussa和Dupont公司的丙烯醛水合加氢法。环氧乙烷羰基化加氢法(中国专利CN1201407A)采用环氧乙烷在钴基催化剂下与合成气生成3-羟基丙醛,再将3-羟基丙醛与氢气在氢化催化剂作用下加氢生成1,3-丙二醇的方法。丙烯醛水合法(中国专利CN93114516.3)采用气态甘油水合物在固体酸催化剂下脱水生成丙烯醛,生成的丙烯醛在酸性催化剂作用下水合生成3-羟基丙醛,生成的3-羟基丙醛在常规加氢催化剂下加氢制备1,3-丙二醇,同时副产1,2-丙二醇。上述工业生产工艺复杂,环境污染严重,所得1,3-丙二醇含有杂质,需进一步净化处理。
文献(Appl.Microbiol.Biotechnol.1992,36,592-597)报道了一种采用Clostridiurn菌种生物转化制备1,3-丙二醇的方法,可以在29h后将110g/L的甘油溶液转化得到56g/L的1,3-丙二醇,该方法受到生物新陈代谢活性的影响,生产效率低,并且由于产物浓度低,纯化分离1,3-丙二醇所需的能耗也很高。文献(Catal.Commun.2008,9,1360-1363)报道了一种在1,3-二甲基-2-咪唑啉酮为溶剂下,甘油氢解制备1,3-丙二醇的方法,此方法1,3-丙二醇的收率为24%。上述反应中采用了有机溶剂作为反应介质,并且所采用的添加液体酸的方法,不符合绿色化学的要求。
甘油直接氢解制备1,3-丙二醇近年来得到了极大关注,因为它工艺简单,原料廉价。但是由甘油直接氢解制备1,3-丙二醇的反应串联反应和并联反应并存,1,3-丙二醇作为中间产物,它的生成首先由甘油脱掉羟基生成碳正离子,而脱去中间羟基生成的碳正离子要更稳定,是动力学优先的,而其后生成的羟基丙醛却在热力学上不稳定,二者之间的相互竞争也是生成1,3的关键。1,3-丙二醇的生成机理使得1,3-丙二醇的高效制备存在很大的挑战。
发明内容
本发明提供一种甘油直接氢解制备1,3-丙二醇的催化剂及其制备方法,与现有技术相比,该发明技术在非常宽广的反应条件窗口下,具有很好的1,3-丙二醇的选择性,有效降低了1,2-丙二醇的生成。
本发明专利提供一种甘油氢解制备1,3-丙二醇的催化剂,催化剂载体为水热或溶剂热法合成的Nb或/和Ta掺杂的氧化钨,掺杂金属质量含量为W重量的0.01%-30%;活性组分为铂族金属Pt或/和Pd,活性组分的质量含量为催化剂重量的0.01%-10%。
本发明所述催化剂的载体Nb或/和Ta掺杂的氧化钨的制备方法为:
将钨和铌或/和钽的前驱体按比例(1:0.0001~0.3)溶于溶剂中,待其完全溶解后将溶液转移入带有内衬的水热釜中,将此水热釜在预热好的40-200℃烘箱内放置6h-1周,然后自然冷却至室温,抽滤后用无水乙醇和去离子水先后洗涤数次,然后常规干燥、冷冻干燥或真空干燥载体Nb或/和Ta掺杂的氧化钨。
采用浸渍法制备催化剂。用氯铂酸或/和氯钯酸溶液浸渍Nb或/和Ta掺杂的氧化钨载体担载活性组分Pt或/和Pd,常规干燥、冷冻干燥或真空干燥后,于100-600℃下H2还原,制得催化剂。
催化剂应用于甘油水溶液氢解制备1,3-丙二醇反应中,反应条件如下:反应是在间歇式釜式反应器中进行,甘油水溶液质量浓度为1-99.9%,反应温度为100-300℃,优选为110-200℃,甘油与催化剂反应时间为0.5-50小时,优选为6-24小时。
本发明与现有技术相比,可以提高甘油氢解制备1,3-丙二醇的选择性,提高甘油转化率,有效抑制1,2-丙二醇的生成,并拓宽反应压力窗口,提高稳定性。
附图说明
图1载体Nb-氧化钨的形貌:a,c为0.1%Nb-氧化钨载体形貌;b,d为2%Nb-氧化钨载体形貌。
具体实施方式
实施例1-Nb-氧化钨载体的制备
采用溶剂热法制备Nb-氧化钨(Nb:W=0.1%,2%,5%)载体,具体制备步骤为:将WCl6和NbCl5(1:0.001~0.1)溶于无水乙醇中,待WCl6和NbCl5完全溶解后将黄色透明溶液迅速转移入带有内衬的水热釜中,此水热釜在预热好的160℃烘箱内放置6-36h(在此为24小时),然后自然冷却至室温,用无水乙醇和去离子水先后洗涤3次,然后放入50℃真空干燥箱干燥得载体Nb-氧化钨。其形貌见附图1。
实施例2-催化剂的制备
将氯铂酸溶液等体积浸渍到Nb-氧化钨载体上,室温阴干,Pt的担载量为2%,50℃烘箱真空干燥6h后,氢气活化,活化条件为300℃,氢气流量为60ml/min,活化时间为1h,制得2%Pt/Nb-氧化钨催化剂。
实施例3-催化剂性能测试
选用间歇式反应釜,甘油水溶液质量浓度为5%(溶液共12g),催化剂量为0.3g(催化剂与甘油质量比为1:2),反应温度为160℃,反应压力为1MPa,反应时间为12h。测试结果见表1.
实施例4-催化剂性能测试
选用间歇式反应釜,甘油水溶液质量浓度为5%(溶液共12g),催化剂量为0.3g(催化剂与甘油质量比为1:2),反应温度为160℃,反应压力为5MPa,反应时间为12h。测试结果见表1.
表1 甘油氢解制备1,3-丙二醇的催化性能
*其他包括少量甲烷,乙烷,丙烷,甲醇,乙醇,乙二醇,丙酮,羟基丙酮,总体物料守恒。
Claims (9)
1.一种甘油氢解制备1,3-丙二醇的催化剂,其特征在于:所述催化剂载体为过渡金属掺杂的氧化钨材料,活性组分为铂族金属,或铂族金属及其助剂;
过渡金属掺杂的量为W重量的0.01%-30%,铂族金属为Pt或/和Pd,铂族金属的含量为催化剂重量的0.01%-10%。
2.根据权利要求1所述的催化剂,其特征在于:助剂为Mo、Au、Fe、La、Al中的一种或二种以上,其重量为铂族金属重量的0.01%-0.5%。
3.根据权利要求1所述的催化剂,其特征在于:掺杂的过渡金属为Nb或/和Ta。
4.根据权利要求2所述的催化剂,其特征在于:过渡金属掺杂的氧化钨采用水热法或溶剂热法制备获得;
将钨、与铌或/和钽的前驱体溶于溶剂中,待其完全溶解后将溶液转移入带有内衬的釜中,将此釜在预热好的40-200℃烘箱内放置6h-1周,然后自然冷却至室温,抽滤后用无水乙醇和去离子水先后洗涤2-8次,然后干燥得载体Nb或/和Ta掺杂的氧化钨。
所选溶剂为水、乙醇、正丙醇、异丙醇、或丙酮中的一种或二种以上。
5.根据权利要求4所述的催化剂,其特征在于:干燥方式为常规干燥、冷冻干燥或真空干燥。
6.一种权利要求1-5所述催化剂的制备方法,其特征在于:催化剂活性贵金属的担载方法为等体积浸渍法、过量浸渍法、真空浸渍法或离子交换法。
7.根据权利要求6所述催化剂的制备方法,其特征在于:催化剂的还原温度为100-600℃;所选铂族金属为Pt或/和Pd。贵金属前体为氯铂酸、氯钯酸等溶液,溶液摩尔浓度0.05-5M。
8.一种权利要求1-5所述催化剂的应用,其特征在于:所述催化剂用于甘油氢解制备1,3-丙二醇反应中,反应原料为甘油水溶液,质量浓度范围为1-99.9%。
9.根据权利要求8所述催化剂的应用,其特征在于:氢气压力为0.1-10MPa,反应温度为100-300℃。
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