CN102105219A - 二氧化硅承载催化剂上的金属铂及其制备方法 - Google Patents
二氧化硅承载催化剂上的金属铂及其制备方法 Download PDFInfo
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- CN102105219A CN102105219A CN2009801285496A CN200980128549A CN102105219A CN 102105219 A CN102105219 A CN 102105219A CN 2009801285496 A CN2009801285496 A CN 2009801285496A CN 200980128549 A CN200980128549 A CN 200980128549A CN 102105219 A CN102105219 A CN 102105219A
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Classifications
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Abstract
本发明是改进的制备催化剂的方法以及通过所述方法制备的催化剂,所述方法用于经水成沉积沉淀制备非均相、负载型氢化催化剂,所述催化剂包括VIII A族金属和催化剂载体(例如,SiO2,具有亲水或疏水表面)。
Description
本申请是要求2008年5月22日提交的题为“METHOD FOR PREPARING A HETEROGENEOUS,HIGH-ACTIVITY PLATINUM-CONTAINING,SUPPORTED HYDROGENATION CATALYST”的美国临时专利申请61/055,254的优选权的非临时申请,其教导在此引入作为参考,在下文如同全文复制。
本发明总地涉及制备催化剂的方法,特别是用于使聚合物(特别地为包含芳环的聚合物)氢化的非均相催化剂。包含芳环的说明性聚合物包括乙烯基芳族均聚物(例如,聚苯乙烯)和苯乙烯类嵌段共聚物(SBC),所述后者如苯乙烯-异戊二烯-苯乙烯(SIS)三嵌段共聚物、苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物、苯乙烯-丁二烯-苯乙烯-丁二烯-苯乙烯(SBSBS)五嵌段共聚物或苯乙烯-异戊二烯-苯乙烯-异戊二烯-苯乙烯(SISIS)五嵌段共聚物。这种方法特别地包括使用水成沉积-沉淀技术,而非使用非水成始润技术或水成始润技术。这种方法更特别地包括使用二氧化硅(SiO2)(不管是具有疏水表面还是亲水表面)作为催化剂载体和任选的抗减活金属(例如,铼(Re))。本发明也涉及通过这种方法制备的催化剂以及这种催化剂在使含芳环聚合物的芳环双键氢化中的用途。
Hucul的美国专利(USP)6,376,622中披露了非均相、SiO2-负载型金属氢化催化剂以及使用该催化剂使芳族聚合物氢化的方法。所述金属选自镍、钴、铑、钌、钯、铂或其组合。所述催化剂也可以包括抗减活组分或选自铼、钼、钨、钽、铌或其混合物的金属。SiO2具有一定的孔径分布,使得至少(>)95%(百分比)的其孔体积由直径为30纳米(nm)(300埃())至100nm(1,000)的孔限定。芳族聚合物可以为SBC。
USP 6,376,622、USP 6,090,359(Hucul)、和USP 6,395,841(Calverly等)教导,助催化剂(如包含碱金属、碱土金属或镧系元素的化合物)可以用来辅助催化金属分散在SiO2载体上或者在反应过程中辅助稳定这样的催化金属,但是说明使用这样的助催化剂不是优选的。
USP 6,455,656(Hahnfeld等)提供了相对于使用这种助催化剂的类似的教导,但是并未提出使用这样的助催化剂不是优选的。
Hucul的USP 5,110,779披露了非均相氢化催化剂,其可以包括助催化剂以在一些反应中进一步增强催化剂的选择性。Hucul教导,非均相催化剂可以通过以下步骤制备:形成催化金属或金属化合物(如金属盐)在适宜的溶剂介质(如水或醇)中的分散体或溶液、将金属的溶液或分散体与载体物质混合、并移除溶剂介质以得到载体与金属或金属化合物的复合材料。Hucul将包含至多五个碳原子的低级烷醇(例如,甲醇、乙醇或丙醇)包括为代表性的非水稀释剂。
USP 6,090,359(Hucul)教导,SiO2-负载型催化剂可以如USP 5,110,779中所说明的制备,并且补充教导,适宜的金属或含金属化合物可以通过以下方法沉积在载体上:首先通过气相沉积、水成浸渍或非水成浸渍,然后通过煅烧、升华或任何其它常规方法。Hucul引用了Studies in Surface Science and Catalysis,“Successful Design of Catalysts”V.44,pages 146-158(1989)、和Applied Heterogeneous Catalysts,pages 75-123,Institute Francais du Pétrole Publications(1987)。
Hucul(USP 6,090,359)和Calverly等(USP 6,395,841)教导,在浸渍的方法中,适宜的含金属化合物可以是包含下述金属的任何化合物,所述金属将产生可用的氢化催化剂。这些化合物可以是盐、配位络合物、金属有机化合物或共价络合物,但是优选为金属卤化物盐,其中金属氯化物盐是最优选的。典型的金属含量范围为0.1重量百分比(wt%)至10wt%,基于全部SiO2-负载型催化剂的重量。
2007年12月13日提交的美国临时专利公开(USPPP)60/013422(Olken等)披露,经一步的始润法制备这样的非均相氢化催化剂,但是使用含水溶剂而非不含水溶剂。
在通过非水成始润制备的非均相催化剂与通过水成始润制备的那些之间,后者催化剂似乎具有与前者匹配的活性。“活性”表示在指定的温度、压力和聚合物浓度所测量的聚合物氢化的速率,以摩尔芳环每小时每克催化剂的单位计。这种测量法将在下面陈述的实施例中更加详细地描述。
存在以下期望:比通过非水成始润或水成始润制备的催化剂活性高的非均相氢化催化剂,特别是如果这种较高的活性与下列中的至少一种一起发生:成本降低、副产物减少或简化的方法。还存在以下期望:相对于通过非水成始润或水成始润制备的催化剂的效率具有改进效率的非均相氢化催化剂。“效率”指每单位重量的氢化金属的活性。效率的改进可以依次导致催化剂成本的降低、对于任何指定的催化活性程度需要较少的氢化金属。
在一些方面,本发明是经水成沉积沉淀(aqueous deposition precipitation)制备包括VIII A族金属和催化剂载体的非均相氢化催化剂的方法,所述方法包括:
a.通过使VIII A族金属前体从VIII A族金属前体的水溶液沉淀到催化剂载体上,经水成沉积沉淀制备润湿的催化剂载体,润湿的催化剂载体包含沉积并分散在催化剂载体表面上的VIII A族金属前体;
b.将润湿的催化剂载体转化成干燥的催化剂载体;和
c.在足以将VIII A族金属前体转化成其金属态的条件下使干燥的催化剂载体经受还原气氛;还原的VIII A族金属的分散度百分比(percent dispersion)超过(>)25%(例如,≥35%),催化剂的氢化活性表示为>0.1摩尔芳环每小时每克催化剂,优选为≥0.15摩尔芳环每小时每克催化剂,并且更优选为≥0.18摩尔芳环每小时每克催化剂。
所述方法任选地进一步包括中间顺序步骤b1.和b2.,其在步骤b.之后并且在步骤c.之前,步骤b1.包括用抗减活金属前体的水溶液将干燥的催化剂载体润湿以制备均质的润湿的催化剂载体,步骤b2.将均质的润湿的催化剂载体转化为干燥的浸渍的催化剂载体。抗减活金属优选为铼(Re)。
以上的步骤a.在≥60摄氏度(℃)的温度进行。期望地,该温度小于或等于(≤)100℃。在步骤a.中,水溶液的pH优选为8至12,更优选为10至12。
也可以将除了Re之外的金属的前体(例如,选自镧(La)、钡(Ba)、钇(Y)、铌(Nb)、铈(Ce)、钆(Gd)或其混合物的金属的前体)加入到步骤a的水溶液中。该金属优选为La。
在一些方面,本发明是非均相氢化催化剂,所述催化剂包括VIII A族金属和催化剂载体,催化剂的VIII A族金属的分散度百分比>25%,而一氧化碳(CO)吸附≥0.4标准立方厘米CO每克(g)催化剂(scc CO/g-催化剂),优选为≥0.5scc CO/g-催化剂,更优选为≥0.6scc CO/g-催化剂,并且再更优选为≥0.7scc CO/g-催化剂。一旦达到>25%的VIII A族金属分散度百分比,则不需要选择任何特定的VIII A族金属含量或VIII A族金属含量范围。仅从催化金属的成本考虑,只要催化剂在合理的时间段内将聚合物有效地氢化至期望的氢化程度,则较少的催化金属优于较多的催化金属。满意的结果来自≤5wt%的VIII A族金属含量,基于全部非均相氢化催化剂的重量。VIII A族金属含量优选为≤3.5wt%,更优选为≤2.5wt%,并且再更优选为≤2wt%,各wt%基于全部非均相氢化催化剂的重量。
当本申请规定范围时(例如,2至10的范围),除非明确排除,否则该范围的端点(例如,2和10)以及各数值(不管这样的值是有理数还是无理数)都包括在此范围内。
本申请提及的元素周期表是指由CRC Press,Inc.于2003出版和并享有版权的元素周期表。任何提及的族应该为在使用编号族的IUPAC系统的这个元素周期表中所反映的族。
除非指出,从上下文的暗示或技术中的惯例,所有的份和百分比均基于重量。针对美国专利实践的目的,任何专利、专利申请、或本申请参考的公开的内容在此全部引入作为参考(或其等价的US实施方式也引入作为参考),特别是关于本技术领域中的合成技术、定义(不与本申请提供的任何定义不一致)和常识的披露。
“包括”及其派生词不排除任何另外的组分、步骤或过程的存在,而不管本申请是否披露过它们。除非指出,否则经使用“包括”的本申请要求的所有组合物可以包括任何另外的添加剂、辅助物、或化合物(不管是聚合的还是非聚合的)。相反,除了对于操作性能不必要的那些,“基本上由...组成”将任何其它组分、步骤或过程排除在任何以下叙述的范围之外。“由...组成”不包括未特别描述或列出的组分、步骤或过程。除非说明,否则“或”指所列出的单独成员以及其任何组合。
温度可以以华氏温度(°F)及其等价物℃表示,或更典型地,简单以℃表示。
催化剂载体优选地包括SiO2,更优选地为具有一定孔径分布和一定表面积的SiO2。使用American Society for Testing and Materials(ASTM)D-4284-83经水银孔率法以确定孔径分布,并使用ASTM D-4641-87以确定表面积。
催化剂载体包含多个孔。当基质聚合物分子(期望氢化其芳环)在溶液中时,各孔优选地具有尺寸或直径,使得足以在该处提供基质聚合物分子(例如,聚苯乙烯)的入口。催化剂载体孔径优选为≥两倍的基质聚合物分子的孔径,更优选为≥三倍的基质聚合物分子的孔径。催化剂载体优选地具有极少、最优选地不具有阻挡基质聚合物分子的入口但是提供VIIIA族金属的入口的孔。
如果基质聚合物分子是聚苯乙烯,Ness等人的Macromolecules,volume35,pages 602-609(2002)提出,可以使用以下方程估算以nm计的聚苯乙烯分子在良好溶剂中的回转半径(Rg):
Rg=1.2E-2*Mn0.595
在此方程中,回转半径的单位是nm,而数均分子量(Mn)的单位是道尔顿或克每摩尔(g/mol)。Ness等认为环己烷在如170℃的高温是良好的溶剂。以上的方程也似乎提供了对苯乙烯类共聚物的Rg的合理估算。
孔径分布优选为300至10,000(30nm至1,000nm),更优选为300至3500(30nm至350nm),再更优选为350至1000(35nm至100nm),甚至更优选为500至600(50nm至60nm)。对于各孔径分布范围,特别优选的结果来自:当将低于各规定下限(例如,300(30nm))的孔径大小减到最少时,优选为当将低于各规定下限(例如,300(30nm))的孔径大小基本上减到最少时,甚至更优选为基本上排除低于各规定下限(例如,300(30nm))的孔径大小时。上述孔径分布,特别是至多为且包括1,000(100nm)的那些,特别适用于Mn≤100,000的聚合物。较高分子量的聚合物(Mn>100,000)倾向于孔径分布>1,000(100nm)。
表观孔径(APD)的估算上限与表面积(SA)(m2/g)有关,其可以经公式APD(以计)=4x104(PV/SA)计算,其中PV表示以立方厘米每克(cm3/g)计的孔体积。以1cm3/g的PV为例,300(30nm)的APD得到140m2/g的SA,500(50nm)的APD得到80m2/g的SA,而1000(100nm)的APD得到40m2/g的SA。熟练技术人员可以容易计算以上提到的孔径分布以内的任何APD的SA。熟练技术人员知道,催化剂载体可以具有较高的PV(例如,1.2),只要PV不是太大使得相应的催化剂载体物质(例如,SiO2)缺乏足够的结构整体性(即,其太脆)而无法作为可行的催化剂载体。熟练技术人员也知道,实际测量的APD可能会并且通常会稍小于以上公式的预测。
完全亲水SiO2和完全疏水SiO2表示表面羟基基团含量范围的相反端点。完全亲水SiO2具有羟基基团的完全表面饱和度所需的羟基基团含量,,具有4至5个羟基基团每平方纳米(OH/nm2)的羟基基团浓度。完全疏水SiO2具有显著降低的表面羟基基团的含量,如0.5OH/nm2。当SiO2从该范围的一个端点(标称地为完全亲水SiO2端)前进至该范围的另一个端点(标称地为完全疏水SiO2端)时,SiO2变得越来越不亲水,并且最终达到亲水和疏水之间的某点,在该点SiO2的疏水性比亲水性强。针对本发明的目的,既可以使用亲水SiO2也可以使用疏水SiO2。
测量由于羟基基团减少的失重的技术包括使用热重分析仪(TGA)在氮气流下以10℃每分钟的速率将亲水SiO2的样品从室温(标称地为25℃)加热至800℃。从室温至200℃的失重似乎归因于吸附水的减少。200℃至800℃的失重似乎是因为羟基基团的减少。即使在800℃,一些羟基基团仍然残留,因为如果没有同时破坏SiO2的多孔性的话,其很难(如果并非不可能)使表面羟基基团含量降至0OH/nm2。TGA有效地测量了热不稳定羟基基团的含量。作为例证,在以下的“实施例”部分中,二氧化硅A的表面羟基基团含量为4.8OH/nm2,而二氧化硅B的表面羟基基团含量为1.5OH/nm2。Ralph K.Iler在Chemistry of Silica,Chapter 6,John Wiley,New York(1979)中提供了很多关于SiO2的信息。
按本申请所描述制备的非均相氢化催化剂包括VIIIA族金属。VIIIA族金属包括镍、钴、铑、钌、钯、铂、或其组合。针对本发明的目的,铂(Pt)提供了优选的氢化结果,不管是单独使用或是与助催化剂金属(例如,镧(La)或铌(Nb)组合使用。如果期望,在VIII A族金属(特别是Pt)在催化剂载体上沉积之后,可以加入抗减活金属(例如,铼(Re))。
适宜的催化剂载体包括各种可从商业上购买到的SiO2,其在以下标题为“实施例”的部分进行描述。
将VIIIA族金属(特别是铂)引入到负载型催化剂中优选地经催化前体物质(优选为酸或酸式盐)进行。对于Pt,前体物质优选为水溶性Pt盐,更优选为选自下列的水溶性Pt盐:氯铂酸(CPA)、硝酸四胺铂(PAN)、六羟基铂酸(hydrogen hexahydroxyplatinate,HHP)、和四氯铂酸铵(ATP)。对于钯(Pd),前体物质也是水溶性盐,优选为四氯钯酸铵(ATPd)。
优选地,VIII A族金属前体含量的存在量足以提供降低的VIII A族金属含量≤5wt%,基于全部非均相氢化催化剂的重量,其中分散度百分比≥25%。VIII A族金属含量更优选为≤3.5wt%,再更优选为≤2.5wt%,并且甚至更优选为≤2wt%,其中低至0.55wt%的含量提供非常满意的结果,各wt%基于全部非均相氢化催化剂的重量。
说明性的优选的VIII A族金属含量包括0.58wt%、0.78wt%、0.84wt%、0.89wt%、0.9wt%、0.92wt%、0.93wt%、1wt%、1.3wt%、1.33wt%、1.36wt%、1.6wt%、1.74wt%、1.8wt%、1.9wt%、和2wt%,其各自用于以下的实施例部分。分散度百分比可以是任何导致以上VIII A族金属含量的百分比。这样的话,其理论上可以高达100%,但是较低的分散度百分比(如40%至≤75%)更为常见并且提供可接受的结果,特别是以相对低的VIII A族金属含量。
USP 6,376,622教导,适宜的抗减活金属包括铼、钼、钨、钽、铌或其混合物。当使用抗减活金属并且针对本发明的目的这种使用是任选的时,铼代表了优选的抗减活金属。高铼酸、高铼酸水溶液和高铼酸铵组成优选的抗减活金属前体。当使用时,铼必需经单独的步骤加入,优选地在VIIIA族金属(特别是铂)的沉积-沉淀之后加入。铼适宜地通过始润加入。
当使用时,优选地,抗减活金属或组分的存在量为,在将该催化剂暴露于聚合物组合物的极性杂质之后足以显著抑制VIIIA族金属组分的减活,本申请将该存在量称为减活抑制量。VIIIA族金属的减活的证据在于,显著降低的氢化反应速率。这可以通过以下进行例证:在相同条件以及在极性杂质存在的情况下,将混合的氢化催化剂与仅包含VIIIA族金属组分的催化剂进行比较,其中所述仅包含VIIIA族金属组分的催化剂的氢化反应速率小于75%的由混合的氢化催化剂所达到的速率。
实施例
以下的实施例说明但不限制本发明。所有的温度以℃计。阿拉伯数字指示本发明的实施例(Ex),照字母次序的大写字母指示对比例(Comp Ex或CEx)。
Ex 1-使用亲水SiO2的制备方法
将9.9克(g)具有亲水表面的SiO2(下文称为“二氧化硅A”)(CARIACTTMQ-50 SiO2,500(50nm)至600(60nm)的孔径大小范围,490(49nm)的测量APD(相较于620(62nm)的计算的APD),1.2cm3/g的PV,67μm的中值粒度,78m2/g的SA,Fuji Silysia)置于250毫升(ml)圆底烧瓶中并加入100ml的0.5摩尔(M)氢氧化铵溶液,使用高架搅拌器搅拌烧瓶的内容物以形成淤浆。将溶于10ml水中的0.245g氯钯酸(CPA)盐加入到淤浆中。该淤浆的pH为10.8。为烧瓶装上回流冷凝管,然后伴随着连续搅拌将混合物加热至90℃的设定温度。在设定温度保持搅拌,并然后将烧瓶内容物的冷却至室温。烧瓶内容物的pH为10.2。
使用真空过滤和布氏漏斗将淤浆的固体组分与淤浆的液体组分分离。用100ml等分的去离子(DI)水将该固体组分洗涤三次。在以100℃的设定温度操作的强制空气对流烘箱中干燥洗涤的固体。洗涤并干燥的固体包含小于约0.05wt%的氯和小于3wt%的水,各wt%基于洗涤并干燥的固体的总重量。
将2.75g干燥过的洗涤的固体置于外径(O.D.)为一英寸(2.54厘米(cm))的石英管中的烧结石英料顶部,然后将该管及其内容物置于垂直管式炉中。使氮气向下通过干燥过的浸渍的SiO2达30分钟。通过以下步骤将干燥过的浸渍的SiO2转化为还原的活化催化剂:首先用氢气含量为5体积百分比(vol%)的改进的氮气流替代氮气,而同时将管式炉及其内容物在两小时的阶段内加热至200℃的设定温度。在冷却至室温之前,继续在200℃的设定温度将管式炉及其内容物加热另外两小时。用纯氮气替代改进的氮气流并使纯氮气流动通过活化催化剂30分钟,然后将活化催化剂从石英管中移走,将其放入瓶子中并密封该瓶。
所述活化催化剂的计算组成为,在SiO2载体上的1.0wt%的Pt,其假设所有的Pt均沉积在载体上。中子活化分析(NAA)显示,%Pt(Pt的百分比含量)为0.91%。这种物质表现了0.72cc CO/g-催化剂的一氧化碳吸附,其得到的金属分散度为69.1%。
将0.89g活化催化剂与以13.7wt%聚苯乙烯(50,000的数均分子量或Mn,54.8克(g)或0.527摩尔的芳环)在环己烷溶剂中的400g溶液置于一升(1L)搅拌式反应器(Pressure Products Industries)中,基于聚苯乙烯和环己烷的总重量。首先以氮气、然后以氢气吹扫反应器顶部空间以便从反应器除去空气和湿气。将反应器内容物加热至160℃的设定温度,同时加入氢气,使得其加入量足以建立600磅每平方英寸表压(psig)(4137千帕斯卡(KPa))的反应器压力。继续加热和加入氢气直至反应器压力保持在600psig(4137KPa)并且基本上不再加入氢气。使反应器内容物重新回到环境温度和压力(大气压力(14.7psig或101KPa),然后回收反应器内容物。
通过下列确定聚苯乙烯芳环的氢化转化率或程度:比较反应器内容物的峰值接近260纳米(nm)的吸收光谱带与未氢化的聚苯乙烯溶液(例如,氢化之前的聚苯乙烯溶液)的吸收光谱带,其中各吸收光谱带是使用UV-Vis分光光度计(LAMBDATM EZ210,Perkin Elmer)经紫外-可见(UV-Vis)光谱法所确定的。转化率为100%,基于氢化之前的芳环含量。
作为比较催化剂性能的方法,确定在当50%的存在于聚苯乙烯溶液中的芳环被氢化时的时间点的氢化速率。包含0.527摩尔聚苯乙烯的溶液的耗氢量为1.58摩尔或3.19g。这表示,当耗氢量合计达1.59g时,苯乙烯芳环氢化达到50%的程度。计算以摩尔氢化的芳环每小时每克催化剂(摩尔/小时/克催化剂)的单位计的这点的氢化速率。所计算的速率为0.458摩尔芳环每小时每克催化剂。
Ex 2至Ex 45
重复Ex 1,所不同的是以下表I中所示的变化。二氧化硅B是疏水SiO2,其表面积(SA)为58m2/g,平均孔径(APD)为759埃()(76纳米(nm)),孔体积(PV)为1.1cm3/g,中值粒度为70μm,表面羟基浓度为1.5OH/nm2,基于加热至800℃的失重的测量值。“二氧化硅C”,即二氧化硅A的变体,以CARIACTTM Q-50C从商业上购自Fuji Silysia(350的测量的APD(相较于550的计算的APD),0.83cm3/g的PV,60μm的中值粒度,62m2/g的SA)。“二氧化硅D”,即二氧化硅A的另一种变体,以CARIACTTM Q-60C从商业上购自Fuji Silysia(400的测量的APD(相较于800的计算的APD),0.83cm3/g的PV,60μm的中值粒度,47m2/g的SA)。“二氧化硅E”,即二氧化硅A的再另一种变体,以CARIACTTM Q-50C SP从商业上购自Fuji Silysia(350的测量的APD(相较于900的计算的APD),0.92cm3/g的PV,30μm的中值粒度,47m2/g的SA)。“二氧化硅F”是二氧化硅A的进一步的变体,其以CARIACTTM Q-50由Fuji Silysia提供,并且在空气中将其煅烧至600℃,通过去除其表面羟基基团使这种亲水SiO2变得疏水(490的测量的APD(相较于600的计算的APD),1.2cm3/g的PV,60μm的中值粒度,78m2/g的SA)。对于大多数催化剂,使用中子活化分析来检验得到的金属负载。然而,许多样品以星号以及标称或目标金属负载(而非其测量值)标示。作为通则,测量的金属负载典型地稍低于目标金属负载。根据该原理,未经中子活化分析的样品的Pt分散度的估算可能低于实分散度(基于等于标称或目标金属负载的金属负载)。
表I的数据证明,良好的催化剂可以通过以下使用多种铂盐的方法制备:使用多种碱以影响金属在多种SiO2载体物质上的沉淀。在几种情况下,催化剂活性比预期的要低(例如,Ex 2相较于Ex 8),其原因尚不明显。低于预期催化剂活性的可能原因包括:在沉积-沉淀反应的过程中低于期望程度的pH或温度控制、和关于催化剂还原的问题(例如,相对于促进最佳还原的温度而言过高或过低的温度;或由如包含碱金属的物质或包含氮(N-)、硫(S-)、或磷(P)的物质造成的样品污染,其任何一种都可作为氢化催化剂的毒剂)。然而,该制备方法通常制备出具有高金属分散度百分比和良好氢化活性的催化剂。CEx F的实验(其中使用氢氧化钠使四氯钯酸盐沉淀)得到无可测量活性的Pd催化剂。尽管数据显示了良好的Pd分散度,但是在如表I所示的条件下不存在氢化活性。催化剂制备参数、组成和操作条件中的一种或多种的改变可以得到一些可检测程度的氢化,其中所述氢化以Pd作为VIII族金属。
Ex 46至Ex 54和CEx A
重复Ex 1,所不同的是以下表II中所示的变化,所述变化包括将铼(Re)(典型地为高铼酸(HReO4))与Pt一同加入。在这些实施例中,比起沉淀,Re似乎更易留在溶液中。因此,尽管良好的催化剂产生自这种方法,但是在初始沉积沉淀步骤加入Re的方法并不存在实质优势,因为Re并未以任何显著程度被引入到最终得到的催化剂中。
对用于表II的催化剂的检测表明其中并无Re。由此,可以得出结论,即Re仍然留在溶液中。Re在溶液中的存在似乎可作为pH缓冲物质,其会降低所加入碱的效果,从而降低Pt在载体上的沉淀量。
表II中的数据证明,在加入Pt的同时加入Re不存在优势。然而,表II的催化剂确实在氢化中起到令人满意的作用。
Ex 55至Ex 62
重复Ex 1,所不同的是以下表III中所示的变化。所述变化包括SiO2载体的类型、VIII A族金属(此情况下为Pt)的量、以及将硝酸镧水合物加入到水中作为镧前体并在加入VIIIA族金属前体(CPA)的同时加入铌(Nb)。Ex 60和Ex 62展示了标称%Pt,因为并无对Ex 60和Ex 62的元素分析。
表III中的数据证明,经沉积-沉淀引入La或Nb并无优势。
CEx B至CEx K
重复Ex 1,所不同的是以下表IV中所示的变化,提供经加入脲引起的Pt沉淀。在一些由脲制备的物质中,pH接近中性而非碱性结束,因此可能发生最小程度的Pt沉淀。同样,当使用非常低的脲浓度时,通常得到较差的催化剂。尽管活性催化剂可以通过以脲作为碱的沉积沉淀方法制得,与使用普通的无机碱(如氢氧化铵和氢氧化钠)相比,这种方法并无优势。
表IV中的数据证明以下情形:在脲分解的条件下,pH由低开始并随着加热而增加,从而将氨水均匀地释放在溶液中。当相对于0.1M的较低值脲浓度为1M时,Pt沉淀似乎是最佳的。与阴离子前体(如CPA)相比,阳离子Pt盐(例如,PAN)似乎更有效地促进Pt沉积。相对于氢氧化铵,使用脲似乎并非优选的,因为当使用Pt络合物(例如,CPA、PAN、和ATP)时,延迟的pH变化并未增加任何实质性的益处,所述Pt络合物在室温与碱的反应缓慢并且需要加热至较高温度(例如,60℃至90℃)才能有效地使Pt沉淀在SiO2基质上。
Ex 63-在后续步骤通过始润加入Re组分的制备方法
将5.0g Ex 1的洗涤并干燥的固体置于空盘中。逐滴地加入7.5ml包含0.034g HReO4的溶液,同时使用刮勺进行手动搅拌以促进均匀变湿。在水溶液加入完成之后,继续搅拌2至4分钟,得到一批均质的润湿SiO2。
在通风橱中,使均质的润湿SiO2在环境温度(标称地为25℃)风干过夜,然后将其置于以110℃的设定温度操作的强制热空气烘箱中干燥两小时,得到一批干燥过的浸渍的SiO2。
如Ex 1,将2.75g干燥过的洗涤的固体转化为还原的活化催化剂,所不同的是使用175℃而非200℃的设定温度。在还原之后,通过中子活化分析,该固体包含0.93wt%的Pt和0.48wt%的Re。其表现了0.45cc/g的CO吸附,这与41.7%的分散度百分比相对应。其提供测量的氢化速率为0.185摩尔芳环每小时每克催化剂。
Ex 64至Ex 74
重复Ex 63,所不同的是如以下表V中所示的变化。
Ex 63至Ex 74证明,Re的加入可以在第二浸渍步骤中进行,从而得到具有适度活性的催化剂。Hucul(USP 6,376,622)提出,铼(Re)可作为,例如,用于聚合物氢化的Pt催化剂的抗减活组分。这些数据表明,Pt/Re催化剂的两步制备可以提供高的Pt分散度以及合理的催化活性,同时引入了由Re提供的抗减活性。
表V
*nd=未测定
Claims (13)
1.一种经水成沉积沉淀制备非均相氢化催化剂的方法,所述催化剂包括VIII A族金属和催化剂载体,所述方法包括:
a.通过使VIII A族金属前体从所述VIII A族金属前体的水溶液沉淀到催化剂载体上,经水成沉积沉淀制备润湿的催化剂载体,所述润湿的催化剂载体包含沉积并分散在催化剂载体表面上的所述VIII A族金属前体;
b.将所述润湿的催化剂载体转化成干燥的催化剂载体;和
c.在足以将所述VIII A族金属前体转化成其金属态的条件下使所述干燥的催化剂载体经受还原气氛,所述还原的VIII A族金属的分散度百分比为至少25%,所述催化剂的氢化活性为至少0.1摩尔芳环每小时每克催化剂。
2.权利要求1中所述的方法,其进一步包括中间顺序步骤b1.和b2.,其在步骤b.之后并且在步骤c.之前,步骤b1.包括用抗减活金属前体的水溶液将所述干燥的催化剂载体润湿以制备均质的润湿的催化剂载体,步骤b2.将所述均质的润湿的催化剂载体转化为干燥的浸渍的催化剂载体。
3.权利要求1或权利要求2中所述的方法,其中步骤a.在至少60摄氏度的温度进行。
4.权利要求1至3中任一项所述的方法,其中所述水溶液的pH为8至12。
5.权利要求1至4中任一项所述的方法,其中所述催化剂载体是二氧化硅。
6.权利要求1至5中任一项所述的方法,其中所述VIII A族金属是铂,所述VIII A族金属前体是水溶性铂盐。
7.权利要求1至6中任一项所述的方法,其中所述抗减活金属是铼,所述抗减活金属前体是高铼酸。
8.权利要求1或权利要求2中所述的方法,其中所述步骤a.的水溶液进一步包括助催化剂金属前体。
9.一种非均相氢化催化剂,所述催化剂包括VIII A族金属和催化剂载体,所述催化剂的VIII A族金属分散度百分比大于25%、其一氧化碳吸附为至少0.4标准立方厘米一氧化碳每克催化剂。
10.权利要求9中所述的催化剂,其中所述催化剂的VIII A族金属含量为至多5wt%,基于全部非均相氢化催化剂的重量。
11.权利要求9或权利要求10中所述的催化剂,其中所述VIII A族金属是铂。
12.权利要求9至11中任一项所述的催化剂,其进一步包括选自下列金属的抗减活金属:铼、钼、钨、钽、铌或其混合物。
13.权利要求9至12中任一项所述的催化剂,其进一步包括选自下列的金属:镧、钡、钇、铈、钆及其混合物。
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KR20110030472A (ko) | 2011-03-23 |
US20110065572A1 (en) | 2011-03-17 |
EP2293873A2 (en) | 2011-03-16 |
CN102105219B (zh) | 2013-07-31 |
US8912115B2 (en) | 2014-12-16 |
WO2009142926A3 (en) | 2010-01-14 |
JP2011520608A (ja) | 2011-07-21 |
TW201002419A (en) | 2010-01-16 |
WO2009142926A2 (en) | 2009-11-26 |
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