CN112237945B - 一种用于乙炔氢氯化的贵金属原子簇催化剂的制备及应用 - Google Patents
一种用于乙炔氢氯化的贵金属原子簇催化剂的制备及应用 Download PDFInfo
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Abstract
本发明提供一种贵金属原子簇和催化剂,原子簇为被有机配体保护的贵金属原子团簇结构,结构式为An(SR)m或An(PB)mCx,A为贵金属,B为和磷(P)配位的有机基团,C为卤素;SR为苯乙硫醇、2‑萘硫醇、一己硫醇或金刚烷硫醇中的至少一种,n=2‑200,m=10‑200,x=2‑20,本发明使用硫醇和三苯基膦(二苯基‑2‑吡啶磷)作为保护剂,S和P原子能够较好地稳定原子簇,阻止其发生团聚,稳定性优良,绿色环保,可循环使用,具备工业应用的可操作性。
Description
技术领域
本发明涉及一种用于乙炔氢氯化反应合成氯乙烯的负载型贵金属原子簇催化剂及其制备方法和应用,属于有机合成中的催化剂制备技术及应用领域。
背景技术
氯乙烯,简称VCM,是合成聚氯乙烯(PVC)的单体。PVC是世界五大通用树脂(PVC、PE、PP、PS和ABS)之一,具有良好的物理机械性能,用于生产建筑、包装和电子材料。随着世界经济的高速发展,人民生活水平的不断提高,对PVC材料的需求量也逐年增大。目前氯乙烯的工业生产主要有3种方法:乙炔法、乙烯法和乙烷法,我国是石油储量较少、煤炭资源相对丰富的国家,所以电石法成为我国PVC生产的主要方法。通过乙炔和氯乙烯反应制备氯乙烯是在在固定床上,基于氯化汞的非均相固体催化剂存在下在气相反应中生成。然而,由于Hg的毒性,对于无汞催化剂的研究越来越多,比如贵金属卤化物,过渡金属等。然而,这些催化剂的使用寿命远远低于基于汞化合物的催化寿命。
早在二十世纪八十年代,英国教授G.J.Hutchings就提出,负载在活性炭上的三价金能够高效催化乙炔氢氯化反应。此报道中指出,其中的活性组分为Au3+,Au3+是通过在王水等氧化剂存在下将载体用该金属的前体浸渍来获得的。然而此后的研究者发现,0价的金同样也具有催化活性。如中国专利CN104707602A公布了用PVA保护的氧化态的Au负载在活性炭上的催化剂,尺寸优选在2nm-6nm之间。中国专利CN104549522A公布了一种以贵金属Pd、Pt、Au为活性组分,S2-、S2O3 2-、SO3 2-等位助剂的非汞催化剂催化乙炔氢氯化。这都是贵金属纳米粒子作为催化剂催化乙炔氢氯化的例子。
传统的纳米颗粒催化剂具有多分散性,这就为从表观催化活性从而联系内在结构增加了很大难度。为了克服这些困难,具有高分散性、高稳定性的原子簇,特别是拥有精确原子数目的原子簇就显得尤为重要。相比纳米粒子(>2nm),原子簇(<2nm)拥有一些独特的性质:(1)空间结构可调:纳米金通常以面心立方结构存在,而金原子簇空间结构受到尺寸和原子数量的显著影响;(2)电子能带量子化:纳米金的电子能带通常连续分布,而金原子簇的电子能带通常非连续和量子化分布。
发明内容
本发明的目的是提供了一种新型的乙炔氢氯化催化剂。贵金属原子簇合成简单,催化乙炔氢氯化反应效率高,能够在将来应用于工业生产中,本发明即基于纳米颗粒对于催化乙炔氢氯化难以建立构效关系的基础上发明了用特定尺寸,特定原子个数的贵金属原子簇催化。
本发明目的是通过以下方式实现的:
本发明一方面提供一种贵金属原子簇,所述原子簇为被有机配体保护的贵金属原子团簇,结构式为An(SR)m或An(PB)mCx,A为贵金属,B为和P配位的有机基团,C为卤素,SR为苯乙硫醇、2-萘硫醇、一己硫醇或金刚烷硫醇中的一种或两种以上,n=2-200,n表示的是贵金属原子个数,m=10-200,m表示有机配体个数,x=2-20,x表示的是卤素原子个数。
基于以上技术方案,优选的,贵金属原子簇为Au或Pt。卤素为Br、Cl、I;和P配位的有机基团为Ph3或Ph2Py。贵金属原子簇催化剂粒径尺寸小于2nm。
基于以上技术方案,优选的,贵金属价态为δ+,δ为0~1。
本发明另一方面提供一种负载型贵金属原子簇催化剂,所述催化剂为将上述的贵金属原子簇负载于载体上,负载量为0.5%-2%。
基于以上技术方案,优选的,所述载体为酸处理改性的活性炭。
本发明还提供一种上述贵金属原子簇催化剂的制备方法,具体包括以下实验步骤:
将贵金属前驱体与有机溶剂A混合,然后加入表面活性剂,搅拌15-60min后,加入有机配体,搅拌1-3小时,加入还原剂,20-50℃搅拌反应3-20小时,用有机溶剂B洗涤后,用有机溶剂C溶解去除不溶物,挥发有机溶剂C后,干燥,得到所述贵金属原子簇催化剂;所述表面活性剂的摩尔量为贵金属前驱体的1-3倍,还原剂的摩尔量为贵金属前驱体的5-20倍。
本发明还提供一种上述负载型贵金属原子簇催化剂的制备方法,用浓度为5-15%盐酸常温搅拌24h后得到改性活性炭后,将活性炭分散于有机溶剂D中得到溶液A,将权利要求1所述的贵金属原子簇催化剂分散于溶剂D中,得到溶液B;所述有机溶剂D为二氯甲烷;将溶液A和溶液B混合后,于20-50℃搅拌3-12h后,离心、洗涤,干燥,得到所述催化剂。
基于以上技术方案,优选的,所述贵金属前驱体为相应金属的氯酸。
基于以上技术方案,优选的,所述表面活性剂为四辛基溴化铵(TOAB)、十六烷基三甲基溴化铵(CTAB);所述还原剂为硼氢化钠、柠檬酸钠、乙二醇;所述有机溶剂A为四氢呋喃(THF)、甲醇、乙醇;所述有机溶剂B为甲醇、正己烷、乙醇;所述有机溶剂C为二氯甲烷、乙腈、丙酮。
基于以上技术方案,优选的,所述催化剂应用于乙炔氢氯化反应合成氯乙烯的反应中,反应温度为150-250℃,反应原料为HCl和C2H2;所述HCl和C2H2的摩尔比为1-2:1,空速为0.2-0.8ml g-1min-1。
有益效果
(1)本发明所研究的贵金属原子簇催化剂合成方法简单易行、产率高。
(2)本发明所研究的贵金属原子簇催化剂使用高活性的贵金属作为活性组分,避免了过渡金属的活性不足,满足工业应用的要求。
(3)本发明所研究的贵金属原子簇相比于常用贵金属纳米颗粒,尺寸均一。
(4)本发明所研究的贵金属原子簇催化剂,保护剂为硫醇和三苯基膦(二苯基-2-吡啶磷),S和P原子能够较好地稳定原子簇,阻止其发生团聚。
(5)本发明所研究的贵金属原子簇催化剂,稳定性优良,绿色环保,可循环使用,具备工业应用的可操作性。
附图说明
图1为实施例1制备的Au25/AC透射电子显微镜图(TEM)。
图2为实施例2制备的Au11/AC透射电子显微镜图(TEM)。
图3为实施例3制备的Au144/AC透射电子显微镜图(TEM)。
图4为实施例4中三个催化剂光电子能谱图(XPS)。
图5为实施例5中催化剂的选择性和转化率图。
图6为实施例6中催化剂的选择性和转化率图。
图7为实施例7中催化剂的选择性和转化率图。
具体实施方式
下面结合附图及具体实施案例来对本发明作进一步的详细说明。
实施例1
Au25(PhC2H4S)18/AC催化剂的制备
称量60mg的HAuCl4·4H2O加入到50mL三口瓶中,加入15mL THF,溶液为金黄色。加入TOAB 92mg(TOAB:HAuCl4·4H2O=1.16mol:1mol),溶液由金黄色慢慢加深为橙红色。搅拌30min后,加入PhCH2CH2SH 97μL(PhCH2CH2SH:HAuCl4·4H2O=5mol:1mol),25℃搅拌一小时,加入NaBH4(4mL冰水)55mg(NaBH4:HAuCl4·4H2O=10mol:1mol)。搅拌三小时,停止反应。用正己烷和甲醇洗产物,沉淀用二氯甲烷溶解,去除不溶物,干燥后得到Au25(PhC2H4S)18。
用二氯甲烷分散盐酸处理后的活性炭,滴加溶于二氯甲烷的Au25(PhC2H4S)18,25℃过夜搅拌,离心干燥得到Au25/AC。
如图1为实施例1制备的Au25/AC透射电子显微镜图,金颗粒的直径为1.3nm左右。
实施例2
Au11(PPh2Py)7Br3/AC催化剂的制备
称量240mgHAuCl4和306mgPPh2Py,加入0.0105mL H2O,溶剂为乙醇,25℃下搅拌9.5h后,乙醇洗后干燥得到AuI(PPh2Py)Cl。称量40mg[AuI(PPh2Py)Cl]和85mg四正辛基溴化铵(TOAB:HAuCl4·4H2O=1.16mol:1mol)溶于10mL乙醇中于圆底烧瓶中搅拌(600rpm/min),接着把NaBH4(15.2mg,NaBH4:HAuCl4·4H2O=5mol:1mol)溶于1mL的乙醇,缓慢滴加进去。反应12h后,将混合物倒入10mL水中,通过4000rpm的离心机离心得到黑色固体,用正己烷/二氯甲烷(v/v=5/1)洗涤几次以除去过量的PPh2Py配体和TOAB。最后,将以上所得沉淀用2mL甲醇萃取,再次离心(10000rpm,5min)以除去不溶物,所得溶液经旋转蒸发仪干燥后得到Au11(PPh2Py)7Br3。
用二氯甲烷分散盐酸处理后的活性炭,滴加溶于二氯甲烷的Au11(PPh2Py)7Br3,25℃过夜搅拌,离心干燥得到Au11/AC。
如图2为实施例1制备的Au11/AC透射电子显微镜图,金颗粒的直径为1.2nm左右。
实施例3
Au144(C6H13S)60/AC催化剂的制备
称量60mg的HAuCl4·4H2O加入到50mL三口瓶中,加入15mL甲醇,溶液为金黄色。加入TOAB 92mg(TOAB:HAuCl4·4H2O=1.16mol:1mol),溶液由金黄色慢慢加深为橙红色。搅拌30min后,加C6H13SH 87μL(C6H13SH:HAuCl4·4H2O=5mol:1mol),25℃常温搅拌一小时,加入NaBH4(4mL冰水)55mg(NaBH4:HAuCl4·4H2O=10mol:1mol)。25℃搅拌五小时,停止反应。用甲醇洗产物,丙酮洗,沉淀用二氯甲烷溶解,去除不溶物,干燥后得到Au144(C6H13S)60。
用二氯甲烷分散盐酸处理后的活性炭,滴加溶于二氯甲烷的Au144(C6H13S)60,25℃过夜搅拌,离心干燥得到Au144/AC。
如图3为实施例3制备的Au144/AC透射电子显微镜图,金颗粒的直径为1.9nm左右。
实施例4
Pt-PhC2H4SH/AC催化剂的制备
称量133.3mg的H2PtCl6·6H2O加入到50mL三口瓶中,加入15mL THF,溶液为黄色。加入TOAB 281.6mg(TOAB:H2PtCl6·6H2O=2mol:1mol)。搅拌30min后,加入PhCH2CH2SH35.6μL(PhCH2CH2SH:H2PtCl6·6H2O=1mol:1mol),25℃搅拌一小时,加入NaBH4(4mL冰水)146mg(NaBH4:H2PtCl6·6H2O=15mol:1mol)。搅拌八小时,停止反应。用正己烷和甲醇洗产物,沉淀用二氯甲烷溶解,去除不溶物,干燥后得到Pt-PhC2H4SH。
用二氯甲烷分散盐酸处理后的活性炭,滴加溶于二氯甲烷的Pt-PhC2H4SH,25℃过夜搅拌,离心干燥得到Pt-PhC2H4SH/AC。
实施例5
用光电子能谱表征实施例1、2、3中催化剂的氧化态。
取50mg实施例1、2、3中的催化剂,压片制XPS样品。
如图4为三个催化剂光电子能谱图,从图中可以看出金的4f7/2处于Au0(83.8eV)和Au+(85.4eV)之间,金的价态为δ+,δ为0~1。
实施例6
Au25(SR)18/AC催化剂的催化活性。
取1g实施例1中的催化剂,装填在内径为8mm的固定床反应器中,空速0.6ml g- 1min-1,HCl:C2H2=1.09,于180℃下反应48h。乙炔初始转化率为88.5%,选择性为100%,48h未降低。
如图5为Au25(SR)18/AC催化剂的催化活性。
实施例7
Au11/AC催化剂的催化活性。
取1g实施例2中的催化剂,装填在内径为8mm的固定床反应器中,空速0.6ml g- 1min-1,HCl:C2H2=1.09,于180℃下反应48h。乙炔初始转化率为89.4%,选择性为100%,48h未降低。
如图6为Au11/AC催化剂的催化活性。
实施例8
Au144(SR)60/AC催化剂的催化活性。
取1g实施例3中的催化剂,装填在内径为8mm的固定床反应器中,空速0.6mlg-1min-1,HCl:C2H2=1.09,于180℃下反应48h。乙炔初始转化率为89.7%,选择性为100%,48h未降低。
如图7为Au144(SR)60/AC催化剂的催化活性。
Claims (6)
1.一种负载型贵金属原子簇催化剂的应用,其特征在于,所述催化剂应用于乙炔氢氯化合成氯乙烯的反应中,所述的贵金属原子簇负载于载体上,负载量为0.5%-2%;所述载体为酸处理改性的活性炭;所述的贵金属原子簇的结构式为A n (SR) m 或A n (PB) m C x ,A为贵金属,B为和磷(P)配位的有机基团,C为卤素;SR为SC2H4Ph、2-萘硫醇、一己硫醇或金刚烷硫醇中的至少一种,n=2-200,m=10-200,x=2-20;所述贵金属为Au或Pt;其中贵金属的价态为δ+,δ为0~1;所述和P配位的有机基团为Ph3或Ph2Py;
所述贵金属原子簇的制备方法,包括如下步骤:
将贵金属前驱体与有机溶剂A混合,然后加入表面活性剂,搅拌15-60min后,加入有机配体,搅拌1-3小时,加入还原剂,常温搅拌反应3-20小时,用有机溶剂B洗涤后,用有机溶剂C溶解去除不溶物,挥发有机溶剂C后,干燥,得到所述贵金属原子簇;所述表面活性剂的摩尔量为贵金属前驱体的1-3倍,还原剂的摩尔量为贵金属前驱体的5-20倍;
所述有机溶剂A为四氢呋喃(THF)、甲醇、乙醇;所述有机溶剂B为甲醇、正己烷、乙醇;所述有机溶剂C为二氯甲烷、乙腈、丙酮。
2.根据权利要求1所述的应用,其特征在于,所述卤素为Br、Cl、I;所述贵金属原子簇粒径尺寸小于2 nm。
3.根据权利要求1所述的应用,其特征在于,所述负载型贵金属原子簇催化剂的制备方法包括如下步骤:
(1)用浓度为5-15%盐酸20-50℃与活性炭搅拌24 h后得到酸处理改性的活性炭,将活性炭分散于有机溶剂D中得到溶液A,将所述的贵金属原子簇分散于有机溶剂D中,得到溶液B;所述有机溶剂D为二氯甲烷;
(2)将溶液A和溶液B混合后,于20-50℃搅拌3-12h后,离心、洗涤,干燥,得到所述催化剂。
4.根据权利要求1所述的应用,其特征在于,所述贵金属前驱体为相应金属的氯酸盐。
5.根据权利要求1所述的应用,其特征在于,所述表面活性剂为四辛基溴化铵(TOAB)、十六烷基三甲基溴化铵(CTAB);所述还原剂为硼氢化钠、柠檬酸钠、乙二醇。
6.根据权利要求1所述的应用,其特征在于,所述乙炔氢氯化反应合成氯乙烯的反应中,反应温度为150-250℃,反应原料为HCl和C2H2;所述HCl和C2H2的摩尔比为1-2:1,空速为0.2-0.8 mL g-1 min-1。
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