CN103476493A - 用于将合成气转化为醇的催化剂 - Google Patents

用于将合成气转化为醇的催化剂 Download PDF

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CN103476493A
CN103476493A CN2011800697142A CN201180069714A CN103476493A CN 103476493 A CN103476493 A CN 103476493A CN 2011800697142 A CN2011800697142 A CN 2011800697142A CN 201180069714 A CN201180069714 A CN 201180069714A CN 103476493 A CN103476493 A CN 103476493A
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D.M.米拉
M.H.麦卡顿
小罗伯特.J.古洛蒂
D.G.巴顿
D.法拉里
B.B.巴丁
刘育
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Abstract

适用于由合成照制备醇的混合物的催化剂包括镍，两种或更多种选自钌、钯、金、铬、铝和锡的金属，和作为促进剂的碱金属或碱土金属中的至少一种的组合。该催化剂可以用于转化合成气的方法，其中主产物是乙醇(EtOH)、丙醇(PrOH)、和丁醇(BuOH)的混合物以及任选的高级醇。

Description

用于将合成气转化为醇的催化剂
在各种方面，本发明总地涉及用于将合成气体(或“合成气”，主要由一氧化碳(CO)和氢气(H2)组成的气体混合物)转化为醇的混合物(例如，乙醇(EtOH)，丙醇(PrOH)，和丁醇(BuOH)，任选地混有高级醇)的催化剂。在各种方面，本发明特别涉及这样的催化剂，其包含镍，和至少(≥)两种或更多种选自钌、钯、金、铬、铝和锡的金属的组合。该催化剂优选地用碱金属或碱土金属促进。
乙醇以及包括乙醇的醇混合物用作燃料和燃料添加剂代替至少一部分基于石油的产品例如汽油，从而减少对石油的需求。用醇代替基于石油的燃料和燃料添加剂可以保留天然资源并改善环境质量，特别是当醇由非石油的原料如生物质或天然气制得时。也可以将乙醇以及包括乙醇的醇混合物转化为有用的化学工业原料烯烃，例如乙烯(C2H6)和丙烯(C3H8)。
转化合成气以制备有机化合物是已知了很多年的。最有用的方法中的一些是将合成气直接转化为醇的那些。这样的转化通常使用非均相催化剂。
美国专利(US)4,762,858教导了使用在载体上的含钼的催化剂将合成气转化为包含乙醇和丙醇的混合醇，其中所述催化剂基本上由以下组成：钼，≥一种选自钍、钇、镧、钆、和镨的金属，和任选的≥一种碱金属或碱土金属。
在一些方面，本发明是合成气转化催化剂，其包含：
a.镍；
b.两种或更多种选自钌、钯、金、铬、铝和锡的金属；
c.包含碱金属或碱土金属中≥一种的促进剂；和
d.≥一种催化剂载体，选自二氧化硅，氧化铝，和氧化镁，或其混合物。
“C2-C4醇”表示一种或多种选自乙醇、丙醇、和丁醇的醇，包括这些化合物的所有已知异构体。
每种合成气转化催化剂的存在形式可以为游离的或组合的。“游离或组合形式”表示金属可以作为游离(或基础)金属、合金、化合物、加合物或其组合存在。代表性的化合物包括氢氧化物，氧化物，硫酸盐，卤化物，碳化物，氰化物，氮化物，硝酸盐，磷酸盐，硼化物，硅化物，硅酸盐，卤氧化物，羧酸盐(例如，乙酸盐和乙酰乙酸盐)，草酸盐，碳酸盐，羰基化合物，氢化物，金属桥接化合物和簇合物，以及其中金属是阴离子或阳离子物类的一部分的化合物。加合物是两种或更多种不同分子的化学加合产物。
对于任何金属，报告以重量百分比(wt%)计的含量，这是通过将作为分子的金属中游离金属含量的质量除以作为分母的所有催化剂组分的质量的比率计算得到。镍和≥两种选自钌、钯、金、铬、铝和锡的金属一起通常各存在量下限为0.1wt%，更优选为0.25wt%，最优选为0.5wt%，特别为1wt%。催化剂金属上限为50wt%，更优选为25wt%，最优选为10wt%，特别为8wt%，各wt%均基于催化剂的总游离金属含量。
将两种或更多种选自钌、钯、金、铬、铝和锡的金属或其混合物的摩尔数除以镍的摩尔数得到其摩尔比。优选的摩尔比为从下限值1比200、更优选为1比1至上限值8比1，更优选为4比1。
碱金属包括锂，钠，钾，铷和铯。碱土金属包括铍，镁，钙，锶和钡。单独的铯或其与钙的组合代表优选的促进剂。
将镍和两种或更多种选自钌、钯、金、铬、铝和锡的金属或其混合物的摩尔数除以碱金属和碱土金属的摩尔数得到其摩尔比。优选的摩尔比为从下限值1比10、更优选为1比3至上限值10比1、更优选为5比1。
促进剂可以作为金属、氧化物、氢氧化物、氮化物、碳化物或作为盐或其组合存在。在合成气转化催化剂制备过程中可以通过多种方法的任一种引入促进剂，例如早期润湿，浸涂或共沉淀。
适宜的催化剂载体包括二氧化硅，α-氧化铝，氧化镁，碳，氧化铬，二氧化钛，氧化锆，和氧化锌。催化剂载体的存在量优选为≥80wt%，更优选为≥90wt%，且至多为(≤)99wt%，更优选为≤98wt%，各wt%均基于所有催化剂组分的总质量。
合成气转化催化剂可以通过本领域已知的多种方法制备，这些方法使得这些组分密切接触，例如早期润湿(一般参见ROBERT L.AUGUSTINE，HETEROGENEOUS CATALYSIS FOR THE SYNTHETIC CHEMIST184-88(Marcel Dekker1996)。在使用早期润湿的情况下，从多种公知的金属的水溶性或溶于溶剂的盐选择待分散在载体上的催化剂金属的来源。将可溶性盐溶解于一定量的溶剂(水溶液、非水溶液、或其组合)中得到溶液；添加足够的溶液以润湿载体、但最多使载体饱和。通过施加热量(任选地在真空下)蒸发溶剂，从而使盐分散在载体上。如必要，则进行重复。
在一种实施方式中，如下制备合成气转化催化剂：在还原性气氛中通过使还原剂例如氢气在环境压力至适当升高的压力(例如，为14.7磅每平方英寸表压(psig)(0.10兆帕(MPa))至600psig(4.14MPa))之间流动而还原最初制备的催化剂前体组合物(通过使用早期润湿技术将镍；≥两种选自钌、钯、金、铬、铝和锡的金属；促进剂；和载体混合而形成)。这种氢气处理的温度下限为250摄氏度(℃)，更优选为330℃。氢气处理的温度上限为1200℃，更优选为700℃。根据需要重复润湿、蒸发和加热步骤以在载体上得到所需浓度的催化性金属物类或促进剂。
在固定床、移动床、流化床、沸腾床或分段床中使用合成气转化催化剂，其中催化剂浓度或活性按与已知催化剂类似的方式从入口到出口变化。使用作为粉末或作为成型形式的催化剂。
由合成气转化催化剂催化的CO和H2的反应产物包括C2-C4醇的混合物与任选的高级醇；其它产物可以包括甲醇，氧化的有机化合物(氧化产物)，烃和CO2。报告相对于CO的产物选择性，以碳原子的摩尔百分比(摩尔%)计。例如，对于将1摩尔CO转化为0.2摩尔甲醇、0.1摩尔乙醇、0.067摩尔正丙醇、0.2摩尔甲烷、和0.2摩尔二氧化碳(CO2)(和0.233摩尔其它产物)的反应，对于这五种反应产物的每一种，报告其选择性为20摩尔%。
对C2-C4醇的选择性优选地高于对甲醇的选择性。在一种实施方式中，对甲醇的选择性小于对C2-C4醇的选择性的一半。在第二种实施方式中，对甲醇的选择性小于对C2-C4醇的选择性的四分之一。优选地，在合成气转化过程中仅形成小部分的除醇之外的其它氧化产物，例如醚，羧酸，酯，酮，醛，和过氧化物。可以将醛氢化成醇。在一种变化中，可以将乙醛氢化成乙醇。在另一种变化中，对所需C2-C4醇产物的选择性为20%或更高。
通常需要各种工艺条件和催化剂组合物来获得这些选择性值。例如，为使用上述制备的还原的催化剂提高优选范围内的转化率，可以改变温度、压力、气时空速(GHSV)、和合成气组成中的一种或多种，从而得到所需结果。当转化率增加时，制得的混合醇的产物分布通常向较高分子量醇迁移。改变循环比和监测循环的组分含量也可以改变选择性。例如，为获得相对于甲醇较多的C2-C4醇，可以将甲醇循环或添加到合成气进料中。改变催化剂金属本身可以得到所需的选择性。例如，在相同的操作条件（其中合成气由95摩尔%或以上的H2/CO摩尔比为1.0的单质氢和一氧化碳气体组成，校正至标准温度和压力(STP)的GHSV为4500小时-1，温度为320℃，压力为500psig(3.4MPa)，没有循环）下，包含在二氧化硅上的Ni-Ru-Al-Ca-Cs和Ni-Ru-Cr-Ca-Cs的催化剂分别产生3摩尔%和9摩尔%的乙醇选择性(基于碳)。
通常，对醇的选择性取决于压力。在标准的操作范围中，在给定温度的压力越高，方法对混合醇的选择性越大。操作压力包括：压力为150psig(1.03MPa))或更高，或其中超过500psig(3.44MPa)的压力是优选的，超过750psig(5.17MPa)的压力是更优选的。特别优选的压力为1,500psig(10.3MPa)至4,000psig(27.6MPa)。当可能时，超过4,000psig(27.6MPa)的压力往往是经济上没有优势的，因为高压容器、压缩机的成本和能量成本。注意这一点，则高达20,000psig(137.9MPa)的压力是可行的，但是10,000psig(68.9MPa)或更小的压力是优选的，5,000psig(34.5MPa)的压力是再更优选的，2,000psig(13.8MPa)至3,000psig(20.7MPa)的压力提供非常令人满意的结果。
用于将合成气转化为混合醇的温度优选为最小值200℃到最大值500℃。最大温度更优选为400℃，仍更优选为370℃。操作的特别优选范围是240℃至350℃。
合成气进料的GHSV是在1小时内在STP穿过给定体积催化剂的H2连同CO气体的体积的量度。GHSV足以制备混合醇并且可以在极宽范围内变化，优选为50小时-1至20,000小时-1。GHSV更优选为≥2000小时-1，仍更优选为≥3000小时-1，但是小于或等于(≤)10,000小时-1，更优选为≤7,500小时-1。在优选的范围内，合成气的转化率通常随GHSV增加而降低。但是，同时，生产率通常提高。通过每单位体积催化剂制得的产物质量测量生产率。
可以将来自反应的流出气体中至少一部分未转化的H2和CO循环至反应器。将循环量表示为循环流中气体的摩尔数与新鲜进料流中气体的摩尔数之比。循环比可以为0至导致形成混合醇产物的任何数目。循环比为0在本发明的范围内，其中优选至少有一些循环。在分离所需醇之后，如果将至少一部分流出气体循环并且其包含未转化的H2和CO，优选除去水、CO2，甚至更优选除去任何形成的烃。甲醇的循环可能有利于C2-C4混合醇的生产。在另一种变化中，可以将一种或多种C2-C4醇或其它醇循环以形成高级醇。
实施例1
将5.6毫克(mg)硝酸镍(II)六水合物(Ni(NO3)2·6H2O)、8.8mg硝酸钯(II)二水合物(Pd(NO3)2·2H2O)、7.0mg硝酸铝九水合物(Al(NO3)3·9H2O)、和250mg粒度为60目(0.250毫米(mm)筛孔)至100目(0.149mm筛孔)的硅胶(SiO2)混入0.31毫升(mL)水中。在70℃在真空下加热混合物2小时，使水蒸发至干燥。将12.4mg硝酸铯(CsNO3)溶解在0.310mL水中，并将该第二混合物与第一混合物混合。在70℃在真空下加热2小时，然后以10℃/分钟的加热速率在静态空气中加热，直到温度达到120℃并保持2小时。最后，以10℃/分钟的加热速率加热至350℃并保持2小时。将完成的催化剂冷却至环境温度。
将0.2mL该催化剂装入1/4-英寸(0.635cm)不锈钢管状反应器。用流动的H2气体在330℃原位还原催化剂150分钟。使用电炉将反应器及其内容物加热到表I中所述的温度。使用预混合的H2和CO将反应器的内部加压到表I中所述的压力。进料气体混合物包含表I中所述比率的H2和CO。以所述GHSV使进料气体混合物穿过反应器以得到反应产物。使反应产物穿过减压阀并流动通过气相色谱(GC)采样点进入冷却的冷凝器。收集并分析来自冷凝器的气态和液态产物。来自反应室的反应产物的GC分析表明存在MeOH、EtOH和其它醇。表I显示关于对乙醇、所有醇(ROH选择性)、烃和CO2的摩尔选择性的产物含量以及反应温度和CO转化率。如本申请使用，“MeOH/ROH”表示归于甲醇的醇的分率，基于碳原子的摩尔基础。
表1
Figure BDA00003864573200051
Figure BDA00003864573200061
实施例2
重复实施例1，但是添加15.2mg乙酰丙酮化钌(III)(Ru(C5H7O2)3)而非Pd(NO3)2·2H2O，和添加7.7mg硝酸铬(III)九水合物(Cr(NO3)3·9H2O)而非Al(NO3)3·9H2O。促进剂是5.0mg硝酸钙四水合物(Ca(NO3)3·4H2O)和12.6mgCsNO3的组合而非单独的CsNO3。
制备醇的实验过程与实施例1相同。结果报告于表2。
表2
温度(℃) 300 320 340
压力(psig) 500 500 500
H2/CO(摩尔比) 1 1 1
GHSV(小时-1) 4500 4500 4500
CO转化率(wt%) 2 2.7 2.1
乙醇选择性(摩尔%) 9 9 15
ROH选择性(摩尔%) 16 15 20
MeOH/ROH(摩尔比) 0.3 0.27 0.22
乙醛选择性(摩尔%) 4 4 6
对烃的选择性(摩尔%) 54 54 63
对CO2的选择性(摩尔%) 24 25 9
实施例1和2中的数据表明，甚至在相对低的压力例如500psig(3.4MPa)或更低可将合成气转化为醇。

Claims (9)

1.合成气转化催化剂，包含：
镍；
选自钌、钯、金、铬、铝和锡的两种或更多种金属；
包含碱金属或碱土金属中至少一种的促进剂；和
催化剂载体，所述催化剂载体选自二氧化硅，氧化铝，和氧化镁，或其混合物。
2.权利要求1的催化剂，其中所述两种或更多种金属包括：钯和铝；或钌和铬；或金和铝。
3.权利要求1的催化剂，其中所述促进剂是铯。
4.权利要求3的催化剂，其中所述促进剂进一步包括钙。
5.制备一种或多种C2-C4醇的方法，所述方法包括在足以将至少一部分合成气转化为乙醇、丙醇和丁醇中至少一种的条件下使合成气与权利要求1-4任一项的催化剂接触。
6.根据权利要求5的制备C2-C4醇的方法，其中所述催化剂在与所述合成气接触之前使用还原剂还原。
7.根据权利要求5或6的制备C2-C4醇的方法，其中将至少一部分合成气转化为甲醇。
8.根据权利要求5或6的制备C2-C4醇的方法，其中将至少一部分合成气转化为乙醛。
9.根据权利要求5或6的制备C2-C4醇的方法，其中所述条件包括500psig(3.4MPa)的最小压力。
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