CN103261127A - 非均相催化剂 - Google Patents

非均相催化剂 Download PDF

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CN103261127A
CN103261127A CN2011800593302A CN201180059330A CN103261127A CN 103261127 A CN103261127 A CN 103261127A CN 2011800593302 A CN2011800593302 A CN 2011800593302A CN 201180059330 A CN201180059330 A CN 201180059330A CN 103261127 A CN103261127 A CN 103261127A
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P.马尼坎丹
S.拉奥
P.K.波拉普拉加达
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Abstract

使用担载的由式RhaAgbSncXdYeOx表示的非均相催化剂将合成气和乙烯的混合物转化为包含至少一种C3氧化物的产物流。在该式中，X是除铑或银以外的至少一种过渡元素，Y是选自碱金属和碱土金属的至少一种元素。

Description

非均相催化剂
相关申请的交叉引用
本申请是非临时申请，要求2010年10月11日提交的题为“HETEROGENEOUS CATALYSTS”的美国临时专利申请61/391,742的优先权，其教导通过参考并入本申请，以下如同全文复制。
技术领域
本发明涉及使用包含在催化剂载体上的金属的组合的非均相催化剂将乙烯和合成气体(“合成气”，一氧化碳(CO)和氢气(H2)的混合物)的进料流转化为包含至少一种三碳(C3)氧化物(例如丙醛或丙醇)的产物流的方法。
背景技术
Steven S.C.Chuang等人在“Role of Silver Promoter in Carbon MonoxideHydrogenation and Ethylene Hydroformylation over Rh/SiO2Catalysts”，Journal of Catalysis，138，536-546(1992)中教导了银(Ag)在硅石(SiO2)-担载的铑(Rh)催化剂上在CO氢化过程中提高形成乙醛(两碳原子(C2)氧化物)的选择性和速率以及在乙烯加氢甲酰化过程中提高形成丙醛的选择性和速率。他们也教导，已知某些促进剂，例如锰(Mn)、锆(Zr)、钛(Ti)、钒(V)和镧(La)的氧化物以及碱金属可增强C2氧化物选择性，而其它促进剂(包括锌(Zn)和铁(Fe))可通过封闭表面位点改善催化剂活性。
Steven S.C.Chuang等人在“C2Oxygenate Synthesis from COHydrogenation on AgRh/SiO2”，Applied Catalysis，第57卷，第241-251页中指出，Ag对形成甲烷和C2+烃的速率的降低大于对形成C2氧化物的速率的降低，导致C2氧化物选择性显著增加。
美国专利(US)4,492,773(Ball等人)教导如下生产C1至C4氧化物：在150摄氏度(°C)至450°C的温度和1巴(100千帕(KPa)至700巴(70,000KPa)的压力使合成气与包含Rh组分和Ag组分的担载混合物的催化剂接触。可以添加的其它金属组分包括铁(Fe)，Mn，Mo，钨(W)，钌(Ru)，铬(Cr)，钍(Th)和锆(Zr)。载体材料包括硅石、氧化铝、硅石/氧化铝、氧化镁、氧化钍、氧化钛、氧化铬、氧化锆、和活性炭。催化剂载体可以由一种或多种非金属活化剂组分活化，所述活化剂组分选自碱金属，Th，Mn，Rh，Fe，Cr，Mo，Zr，铼(Re)，Ag，硼(B)和磷(P)。
发明内容
在一些方面，本发明是将包含合成气和乙烯的进料流转化为包含至少一种三碳氧化物的产物流的方法，所述方法包括：在足以有效将所述进料流转化为所述产物流的条件下使所述进料流与非均相催化剂接触，所述催化剂包括在催化剂载体上的金属的组合，所述金属的组合由通式RhaAgbSncXdYeOx表示，其中X是除铑或银以外的至少一种过渡元素，Y是选自碱金属和碱土金属的至少一种元素，a是0.1毫摩尔/一百克(mmol/hg)至50mmol/hg范围内的实数，b是0.1mmol/hg至50mmol/hg范围内的实数，c是0.1mmol/hg至50mmol/hg范围内的实数，d是0mmol/hg至250mmol/hg范围内的实数，e是0mmol/hg至1500mmol/hg范围内的实数，x是平衡Rh、Ag、Sn、X和Y元素总电荷数所需的大于0的实数，所述催化剂载体是硅石、氧化铝、氧化钛、氧化镁、铝酸镁、和铝酸锌中的至少一种。
具体实施方式
由以上通式表示的金属的组合包括以下物质、基本上由以下物质组成、或由以下物质组成：Rh、Ag、和锡(Sn)任选地与选自以下的至少一种促进剂进一步组合：当d大于0时为X(除银或铑之外的至少一种过渡金属)，当e大于0时为Y(至少一种碱金属或碱土金属)。当d、e或d和e两者为0时，相应元素(对于d为X，对于e为Y)在所述金属的组合中不存在。
将进料流转化为产物流的方法条件包括以下的至少一种：压力为12磅每平方英寸表压(psig)(82.7千帕(KPa))至4,000psig(27.6兆帕(MPa))、优选为20巴(2MPa)至45巴(4.5MPa)，温度为100°C至450°C、优选为280°C至320°C，气时空速(GHSV)为25小时-1(h-1)至25,000h-1、优选为2000h-1至10000h-1，乙烯与一氧化碳与氢气的进料流比率(C2H4:CO:H2)为0.01:10:10至10.0:0.01:0.01，其中该比率为1:1:1时得到非常满意的结果。
除Rh和Ag之外的过渡金属选自元素21至29(钪(Sc)至Cu，元素39(钇(Y)至44(钌(Ru))，46(钯(Pd)，57至79(镧(La)至Au)和从89(锕(Ac)的所有已知元素，这些元素列于元素周期表(在Hawley’s Condensed Chemical Dictionary，Twelfth Edition(1993)的封面内)。优选的过渡金属包括Zn，Fe，Cr，Co，和Ir。
碱金属包括钠(Na)，锂(Li)，钾(K)，铷(Rb)，铯(Cs)和钫(Fr)。碱土金属包括镁(Mg)，铍(Be)，钙(Ca)，锶(Sr)，钡(Ba)和镭(Ra)。当催化剂包括组分Y时，可以使用至少一种碱金属，或至少一种碱土金属，或至少一种碱金属和至少一种碱土金属的组合。
催化剂载体是以下的至少一种：硅石、氧化铝、氧化钛、氧化镁、铝酸镁、镁改性的硅石、镁改性的氧化铝、锆改性的硅石、锆改性的氧化铝、锌改性的硅石、锌改性的氧化铝、和铝酸锌，其中硅石、氧化镁、铝酸镁和氧化铝是优选的载体。
作为另外的选项，可以将碱金属碳酸盐如碳酸钠与由以上通式表示的催化剂组合物混合。碱金属碳酸盐似乎可降低催化剂酸度，这可能能解释为何在本发明至少一些方面过程中促进将烯烃氢化为烷烃的趋势降低。
本发明至少一些方面的方法已经用于制备至少一种C3氧化物。C3氧化物由此可应用于用作生产其它化学品的原料，例如通过将丙醇脱水而制备丙烯。由此丙烯可用作制备多种聚合物材料的原料，所述聚合物材料例如聚丙烯，其在制造制品中的用途颇多。
非均相催化剂提供的乙烯转化率为大于90摩尔百分比(mol%)，基于进料流中乙烯的总摩尔数，以及对C3氧化物的选择性、优选为对丙醇和丙醛(丙醛)的选择性为至少70mol%，基于产物流中产物的总摩尔数。对C3氧化物的选择性优选地有利于丙醇(与丙醛相比)，使得产物流包含的丙醇比丙醛多。
由通式RhaAgbSncXdYeOx表示的非均相催化剂具有的Rh含量为0.1mmol/hg至50mmol/hg、优选为5mmol/hg至30mmol/hg，Ag含量为0.1mmol/hg至50mmol/hg、优选为2mmol/hg至10mmol/hg，Sn含量为0.1mmol/hg至50mmol/hg、优选为0.8mmol/hg至5mmol/hg，X含量为0mmol/hg至222mmol/hg、优选为1mmol/hg至40mmol/hg，Y含量为0mmol/hg至1500mmol/hg、优选为1mmol/hg至500mmol/hg、和O含量由形成的净化合物确定。mmol/hg各自基于Rh、Ag、Sn、X、Y和O的总重量。
阿拉伯数字表示本发明的实施例(Ex)，按顺序的大写字母表示对比实施例(Comp Ex或CEx)。
实施例
CExA：
在10ml玻璃小瓶中，添加包含48.59微摩尔(μmol)(10.17mg)RhCl3·3H2O的水溶液(0.95ml)到0.5g硅石(DavisonTM57，表面积=280±20m2/g)中并使用金属搅拌器在室温搅拌所得混合物。使容器内容物在120°C(在真空下?)经受干燥过夜。用0.475ml包含21.75(μmol)(1.27mg)NaCl的水溶液浸渍干燥的内容物。在室温干燥浸渍的内容物4小时。在空气中在400°C在静态空气中(加热速率为2°C/分钟)煅烧干燥的容器内容物4小时，得到表示为Rh9.718Na4.35/SiO2的催化剂。
使用高压平行固定床反应器(PFBR)(PFBR系统P/N;132088，得自SymyxTMTechnologies Inc)，即包括三个隔室的模反应器(modular reactor)评价催化剂性能，所述三个隔室每个都包含16个反应器管。将各隔室中的管封入到不锈钢钟形玻璃容器中，所述不锈钢钟形玻璃容器能够在与用于各反应的压力相同的压力用氮气(N2)加压。将200微升(μL)催化剂装入到反应器管中，在35巴(3.5MPa)在350°C(加热速率为5°C/分钟)使用90体积%(vol%)氢气(H2)和10vol%N2的气体混合物将催化剂原位还原3小时，每个vol%均基于总气体混合物体积。将催化剂冷却至280°C。
如下测试催化剂：其中压力为35巴(3.5MPa)，温度为280°C、300°C和320°C，使用的进料混合物为42.6vol%的H2、42.6vol%的CO、4.8vol%的乙烯和10vol%的N2，每个vol%均基于总进料混合物体积，以20.8ml/分钟的速率流过催化剂之上。保持温度在320°C，但是增加压力至90巴(9MPa)以评价较高的压力。将温度提高至340°C，但是将压力返回至35巴(3.5MPa)以评价较高的温度。使用西门子工艺GC评价反应器管流出物。重复该催化剂测试周期另外两次，并将以下表1中三次测试周期的平均值报告为测试结果。
CExB
重复CExA，所不同的是用包含23.18μmol(3.94mg)AgNO3和19.11μmol(5.68mg)Zn(NO3)2.6H2O的水溶液(1ml)代替包含RhCl3·3H2O的水溶液。催化剂表示为Ag4.635-Zn3.823-Na4.35/SiO2。
CExC
重复CEx A，但是有所变化。首先，用包含23.18μmol(3.94mg)AgNO3的水溶液(1ml)浸渍硅石，并使其在120°C干燥过夜。第二，用0.475ml包含48.59μmol(10.17mg)RhCl3·3H2O的水溶液浸渍干燥的浸渍的硅石，并使其在100°C干燥4小时。第三，用0.475ml包含21.75μmol(1.27mg)NaCl的水溶液浸渍干燥的两次浸渍的硅石，形成膏体。使膏体经受干燥，首先在真空下在80°C干燥4小时(hr)，然后在120°C在大气压干燥4hr。按照CExA煅烧干燥的膏体，得到表示为Rh9.718-Ag4.635-Na4.35/SiO2的催化剂。
Ex1
重复CEx C，所不同的是添加8.44μmol(1.6mg)氯化亚锡(SnCl2)到包含NaCl的水溶液中，得到表示为Rh9.718-Ag4.635-Sn2.106Na4.35/SiO2的催化剂。
Ex2
重复Ex1，所不同的是将SnCl2的量降低至4.22μmol(0.8mg)并添加19.11μmol(5.68mg)的硝酸锌六水合物(Zn(NO3)2·6H2O)到包含AgNO3的水溶液中，得到表示为Rh9.718-Ag4.635-Zn3.823Sn0.842Na4.349/SiO2的催化剂。
Ex3
重复Ex1，所不同的是添加51.43μmol(13.19mg)的硝酸镁六水合物Mg(NO3)2·6H2O到包含AgNO3的水溶液中，得到表示为Rh9.718-Ag4.635-Zn3.823Mg10.286Sn0.842Na4.349/SiO2的催化剂。
Ex4
重复Ex3，但是有所变化。首先，将AgNO3的量增加至34.77μmol(5.91mg)。第二，将Zn(NO3)2·6H20的量增加至38.22μmol(11.37mg)。催化剂表示为Rh9.718-Ag6.953-Zn7.646-Mg10.286-Sn0.842-Na4.349/SiO2。参见表2的测试结果。
Ex5
重复Ex4，但是将RhCl3.3H2O的量增加至121.475μmol(24.42mg)。催化剂表示为Rh24.294-Ag6.953-Zn7.646-Mg10.286-Sn0.842-Na4.349/SiO2。
Ex6
重复Ex5，但是有所变化。首先，不再添加Mg(NO3)2·6H2O。第二，在煅烧之后，使用研钵和杵将502mg煅烧的干燥膏体与1.1mg碳酸钠(Na2CO3)物理混合。物理混合的催化剂表示为Rh2.5-Ag6.953-Zn7.646-Sn0.842-Na4.349-NC4.717/SiO2。“NC”表示碳酸钠。
Ex7
在装备有搅拌棒的单口玻璃反应器中，在恒定搅拌下在室温(标称25°C)在一小时内添加包含0.0512g RhCl3·3H2O、0.0076g SnCl2·2H2O、0.0157gAgNO3和0.0289g Fe(NO3)3·9H2O的水溶液到2.0g SiO2载体(AerosilTM300，Degussa，表面积=300±30平方米每克(m2/g))中。升高温度并蒸发反应器内容物至干燥。按照CEx A，干燥并煅烧蒸发脱水的粉末，得到表示为Rh9.718Sn1.685Ag4.635Fe3.581/SiO2的硅石-担载的Rh催化剂。参见表3的测试结果。
Ex8
重复Ex7，不同的是用0.013g的Mn(NO2)2替换Fe(NO3)3·9H2O，得到表示为Rh9.718Sn1.685Ag4.635Mn3.64/SiO2的催化剂。
Ex9
重复Ex7，不同的是用0.0308g的Cr(NO3)·9H2O替换Fe(NO3)3·9H2O，得到表示为Rh9.718Sn1.685Ag4.635Cr3.846/SiO2的催化剂。
Ex10
重复Ex7，不同的是用0.0198g的Co(NO3)2.6H2O替换Fe(NO3)3·9H2O，得到表示为Rh9.718Sn1.685Ag4.635Co3.394/SiO2的催化剂。
Ex11
重复Ex7，不同的是用0.0070g的IrCl4·xH2O替换Fe(NO3)3·9H2O，得到表示为Rh9.718Sn1.685Ag4.635Ir1.04/SiO2的催化剂。
表1
Figure BDA00003324129800061
Figure BDA00003324129800071
X*表示转化率；S**表示选择性
表2
Figure BDA00003324129800072
X*表示转化率；S**表示选择性。
表3
X*表示转化率；S**表示选择性，GHSV=6730h-1。
表1-3中的数据证明，包含Rh、Ag和Sn、基本上由Rh、Ag和Sn组成或由Rh、Ag和Sn组成的催化剂组合物表现出可有效转化包含乙烯、一氧化碳和氢气的进料，以制备至少C3氧化物。该数据也表明，当催化剂进一步包括一种或多种选自Zn、碱金属、碱土金属、和过渡金属的另外元素时，催化剂性能改善。优选的过渡金属包括铁，锰，铬，钴和铱。

Claims (3)

1.将包含合成气和乙烯的进料流转化为包含至少一种三碳氧化物的产物流的方法，所述方法包括：在足以有效将所述进料流转化为所述产物流的条件下使所述进料流与非均相催化剂接触，所述催化剂包括在催化剂载体上的金属的组合，所述金属的组合由通式RhaAgbSncXdYeOx表示，其中X是除铑或银以外的至少一种过渡元素，Y是选自碱金属和碱土金属的至少一种元素，a是0.1毫摩尔/一百克至50毫摩尔/一百克范围内的实数，b是0.1毫摩尔/一百克至50毫摩尔/一百克范围内的实数，c是0.1毫摩尔/一百克至50毫摩尔/一百克范围内的实数，d是0毫摩尔/一百克至250毫摩尔/一百克范围内的实数，e是0毫摩尔/一百克至1500毫摩尔/一百克范围内的实数，x是平衡Rh、Ag、Sn、X和Y元素总电荷数所需的大于0的实数，所述催化剂载体是硅石、氧化铝、氧化钛、氧化镁、铝酸镁、和铝酸锌中的至少一种。
2.权利要求1的方法，其中X是选自锌、铁、锰、铬、钴和铱的至少一种元素。
3.权利要求1或权利要求2的方法，其中所述条件包括以下的至少一种：温度为100°C至450°C，压力为12磅每平方英寸表压(psig)(82.7千帕(KPa))至4,000psig(27.6兆帕(MPa))，气时空速(GHSV)为25小时-1(h-1)至25,000h-1，乙烯与一氧化碳与氢气的进料流比率(C2H4:CO:H2)为0.01:10:10至10.0:0.01:0.01。
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