CN100493701C - 一种进行费托合成反应的方法及其专用催化剂 - Google Patents

一种进行费托合成反应的方法及其专用催化剂 Download PDF

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CN100493701C
CN100493701C CNB200710099011XA CN200710099011A CN100493701C CN 100493701 C CN100493701 C CN 100493701C CN B200710099011X A CNB200710099011X A CN B200710099011XA CN 200710099011 A CN200710099011 A CN 200710099011A CN 100493701 C CN100493701 C CN 100493701C
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寇元
颜宁
肖超贤
蔡志鹏
李永旺
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Zhongke Synthetic Oil Technology Co Ltd
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Abstract

本发明公开了一种进行费托合成反应的方法及其专用催化剂。该过渡金属纳米催化剂，包括过渡金属纳米粒子和高分子稳定剂，过渡金属纳米粒子分散在液体介质中形成胶体。本发明进行费托合成反应的方法，是将CO和H2在催化剂作用下进行催化反应，所用催化剂即为本发明过渡金属纳米催化剂。催化剂能够在反应条件下实现三维自由旋转，具有很好的低温活性，在100-200℃下即可催化费托合成，远比现行工业催化剂需要的条件(200-350℃)温和；并且，过渡金属纳米粒子的粒径较小，分布较窄，有利于控制产物的分布；烃类产物容易与催化剂分离，催化剂可实现回收和循环利用，具有广阔的应用前景。

Description

一种进行费托合成反应的方法及其专用催化剂
技术领域
本发明涉及一种进行费托合成反应的方法及其专用催化剂。
背景技术
费托合成反应指一氧化碳和氢气(合成气)在铁、钴、钌等金属催化作用下转化为烃类的反应，其产物分布很宽，从C1(甲烷)开始呈连续分布。由于石油资源日益枯竭，而煤、天然气、生物质等资源相对丰富，从煤、天然气、生物质等出发生产合成气，再由合成气通过费托合成制烃(汽油，柴油等)，可以缓解对石油资源的依赖，对国家安全和社会利益都有很重要的意义。
目前，在现有费托合成反应条件下，希望得到的汽油、柴油(主要是C5+)选择性较低，而不能利用的甲烷选择性偏高；CO转化不完全，需要在尾气中回收利用，从而增加生产成本；反应的温度一般在200-350℃，但是费托合成反应是一个放热反应，高温对反应平衡是不利的，而且容易使催化剂局部过热而烧结；此外费托合成普遍采用块状的熔铁或担载在SiO2等载体表面的铁、钴、钌等催化剂，此类催化剂由于活性组分被束缚在载体的2维表面，不能自由旋转，裸露的催化剂表面积及活性位相对较少，从而降低了反应活性。根据文献报道，催化活性最高的是钌，其次是铁和钴；反应温度基本在200-350℃，体系的总压力为1-50atm左右。虽然，有在100-140℃下非担载的钌催化CO加氢的报道，但是需要的总压力非常苛刻，通常为1000atm(Robert B.Anderson，in“The Fischer-Tropsch synthesis”，pp.104-105，Academic Press，1984)，得到的产物分子量很大，大部分为大于10000的聚乙烯。
发明内容
本发明的目的是提供一种反应速率高、反应温度低的进行费托合成反应的方法及其专用过渡金属催化剂。
该过渡金属纳米催化剂，包括过渡金属纳米粒子和高分子稳定剂，过渡金属纳米粒子分散在液体介质中形成稳定胶体。
过渡金属纳米粒子的粒径为1—10nm；优选为1.8±0.4nm；过渡金属选自Ru、Co、Ni、Fe和Rh中的一种或几种。
该过渡金属纳米催化剂可按如下步骤制备：
将过渡金属盐与高分子稳定剂混合分散于液体介质中，在100—200℃下以H2还原，得到所述过渡金属纳米催化剂。
还原反应的压力为0.1—4.0MPa，反应温度为100-200℃，反应时间为2小时。高分子稳定剂与过渡金属盐的摩尔比为400:1—1:1，过渡金属盐在液体介质中浓度为0.0014—0.014mol/L。常用的过渡金属盐选自Ru、Co、Ni、Fe和Rh中的一种或几种；所述高分子稳定剂为聚乙烯基吡咯烷酮或poly[(N-Vinyl-2-pyrrolidone)-co-(1-vinyl-3-alkylimidazolium halide)](一种共聚高分子，简称[BVIMPVP]Cl，制备方法见J.Am.Chem.Soc.2005，127，9694-9695)；所述液体介质选自水、醇类、烃类、醚类和离子液体，优选为水，乙醇，环己烷，1，4-二氧六环或[BMIM][BF4]离子液体。
本发明进行费托合成反应的方法，是将CO和H2在催化剂作用下进行催化反应，所用催化剂为本发明过渡金属纳米催化剂。
催化反应的温度为100—200℃，优选为150℃。CO和H2的总压力为0.1—10MPa；优选为3MPa。催化反应中，H2/CO的摩尔比为0.5—3：1；优选为0.5、1.0或2.0。
本发明先制备了一种过渡金属纳米催化剂，催化剂是一种纳米级(1-10nm)的金属纳米粒子，可以均匀分散在液体介质中，形成稳定的胶体，该胶体在反应前后不会聚沉。催化剂能够在反应条件下实现三维自由旋转，具有很好的低温活性，在100—200℃下即可催化费托合成，远比现行工业催化剂需要的条件(200-350℃)温和；并且，过渡金属纳米粒子的粒径较小，分布较窄，有利于控制产物的分布；烃类产物容易与催化剂分离，催化剂可实现回收和循环利用，具有广阔的应用前景。
附图说明
图1为本发明钌纳米催化剂的电镜照片和粒径分布图。
具体实施方式
本发明进行费托合成反应主要是利用一种过渡金属纳米粒子催化剂，该催化剂可按照如下过程制备：
将过渡金属盐与高分子稳定剂混合分散于液体介质中，在100—200℃下以H2还原，得到该过渡金属纳米催化剂。
其中，常用过渡金属盐为RuCl3·nH2O、CoCl2·6H2O、NiCl2·6H2O、FeCl3·6H2O、RhCl3·nH2O，当选用不同过渡金属元素的盐时，可以得到混合过渡金属纳米催化剂；高分子稳定剂为聚乙烯基吡咯烷酮等；液体介质选自水、醇类、烃类、醚类和离子液体等，优选为水，乙醇，环己烷，1，4-二氧六环或[BMIM][BF4]离子液体。高分子稳定剂与过渡金属盐的摩尔比为400:1—1:1；过渡金属盐在液体介质中浓度为0.0014—0.014mol/L。
进行还原反应时，优选的压力为0.1—4.0MPa，优选为2MPa；优选的反应温度为150℃，反应时间为2小时。
应用上述催化剂进行费托合成反应，是在催化剂体系中，充入一定压力的H2和CO合成气，在适当温度下即可以开始反应。反应介质即为催化剂所分散的液体介质。
在上述费托合成反应过程中，反应温度在100—200℃之间，优选为150℃；反应压力为0.1—10MPa，优选为3MPa；合成气中，H2/CO的摩尔比为0.5—3：1，优选为0.5、1.0或2.0。
各种反应条件下的产物分布比较一致，主要为正构烷烃，有少量异构烷烃和α-烯烃。在以下的各具体实施例中，产物的典型分布为：C1 3.4-6.3％，C2-C4 13.2-18.0％，C5-C12 53.2-56.9％，C13-C20 16.9-24.2％，C21+ 1.5-4.9％。可用的C5+占到产物总量的76.7-83.4％。
以下结合具体的实施例来描述本发明反应过程。
实施例1、
将73mg RuCl3·nH2O和620mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝20，摩尔比，下同)加入到20ml水中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atm H2下还原2小时，即制得反应用催化剂。制备的钌纳米粒子平均粒径为1.8±0.4nm，钌纳米粒子的透射电镜照片和粒径分布分别如图1a和图1b所示。
将催化剂冷至室温，放出残余气体，然后充入10atm CO，20atm H2，在150℃下反应。反应结果见表1。
实施例2
将73mg RuCl3·nH2O和106mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝3.4)加入到20ml 1，4-二氧六环中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atm H2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atmCO，20atm H2，在150℃下反应。反应结果见表1。
实施例3
将73mg RuCl3·nH2O和106mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝3.4)加入到20ml乙醇中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atmH2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atm CO，20atm H2，在150℃下反应。反应结果见表1。
实施例4
将73mg RuCl3·nH2O和1.4mmol poly[(N-Vinyl-2-pyrrolidone)-co-(1-vinyl-3-alkylimidazolium halide)](简称[BVIMPVP]Cl，按单体分子量为126计算)的甲醇溶液加入到10ml[BMIM][BF4]离子液体中，搅拌混匀，在60℃旋蒸1h，除去甲醇，剩余溶液加入到容积为60ml的高压釜中，在150℃，20atm H2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atm CO，20atm H2，在150℃下反应。反应结果见表1。
实施例5
将73mg RuCl3·nH2O和620mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝20)加入到20ml水中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atmH2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atm CO，5atm H2，在150℃下反应。反应结果见表1。
实施例6
将73mg RuCl3·nH2O和620mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝20)加入到20ml水中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atmH2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atm CO，20atm H2，在100℃下反应。反应结果见表1。
实施例7
将7.3mg RuCl3·nH2O和62mg聚乙烯基吡咯烷酮(聚乙烯基吡咯烷酮：Ru＝20)加入到20ml水中，搅拌混匀，然后加入到容积为60ml的高压釜中，在150℃，20atmH2下还原2小时，即制得反应用催化剂。冷至室温，放出残余气体，充入10atm CO，20atm H2，在150℃下反应。反应结果见表1。
表1.过渡金属纳米粒子在不同溶剂中的费托合成反应活性
 
实施例 反应条件 下降总压力 转化频率(按CO计，摩尔CO/(摩尔Ru·小时))
 
实施例1 聚乙烯基吡咯烷酮：Ru＝20:1，20.0ml水，2.79×10<sup>-4</sup>mol Ru，150℃，20.0atm H<sub>2</sub>，10.0atm CO 26.2atm/14h 6.1
实施例2 聚乙烯基吡咯烷酮：Ru＝3.4:1，20.0ml 1，4-二氧六环，2.79×10<sup>-4</sup>mol Ru，150℃，20.0atm H<sub>2</sub>，10.0atm CO 1atm/8h 0.42
实施例3 聚乙烯基吡咯烷酮：Ru＝3.4:1，20.0ml乙醇，2.79×10<sup>-4</sup>mol Ru，150℃，20.0atm H<sub>2</sub>，10.0atm CO 1atm/10h 0.32
实施例4 [BVIMPVP]Cl∶Ru＝5:1，10.0ml[BMIM][BF<sub>4</sub>]离子液体，2.79×10<sup>-4</sup>mol Ru，150℃，20.0atm H<sub>2</sub>，10.0atm CO 3.2atm/14.3h 0.52
实施例5 聚乙烯基吡咯烷酮：Ru＝20:1，20.0ml水，2.79×10<sup>-4</sup>mol Ru，150℃，5.0atm H<sub>2</sub>，10.0atm CO 8atm/11.5h 2.3
实施例6 聚乙烯基吡咯烷酮：Ru＝20:1，20.0ml水，2.79×10<sup>-4</sup>mol Ru，100℃，20.0atm H<sub>2</sub>，10.0atm CO 3.4atm/15h 0.74
实施例7 聚乙烯基吡咯烷酮：Ru＝20:1，20.0ml水，2.79×10<sup>-5</sup>mol Ru，150℃，20.0atm H<sub>2</sub>，10.0atm CO 6.2atm/15.5h 13
以上结果表明，该过渡金属纳米催化剂在100-150℃就具有好的催化活性，比工业费托催化剂的温度(200-350℃)显著降低。产物中可用的C5+组分含量也较高(76.7-83.4％)，因而该过渡金属纳米催化剂具有很好的工业应用前景。

Claims (15)

1、一种用于费托合成反应的过渡金属纳米催化剂，包括过渡金属纳米粒子和高分子稳定剂，所述过渡金属纳米粒子分散在液体介质中形成稳定胶体；所述过渡金属为Ru、Co、Ni和Fe中的一种或几种；所述高分子稳定剂为聚乙烯基吡咯烷酮或(N-乙烯基-2-吡咯烷酮)-(1-乙烯基-3-烷基咪唑卤盐)共聚物。
2、根据权利要求1所述的过渡金属纳米催化剂，其特征在于：所述过渡金属纳米粒子的粒径为1—10nm。
3、根据权利要求2所述的过渡金属纳米催化剂，其特征在于：所述过渡金属纳米粒子的粒径为1.8±0.4nm。
4、根据权利要求1-3中任一所述的过渡金属纳米催化剂，其特征在于：所述过渡金属纳米催化剂按如下步骤制备：
将过渡金属盐与高分子稳定剂混合分散于液体介质中，在100—200℃下以H2还原，得到所述过渡金属纳米催化剂。
5、根据权利要求4所述的过渡金属纳米催化剂，其特征在于：所述还原反应H2的压力为0.1—4MPa，反应时间为2小时。
6、根据权利要求4所述的过渡金属纳米催化剂，其特征在于：所述高分子稳定剂与过渡金属盐的摩尔比为400:1—1:1；过渡金属盐在液体介质中浓度为0.0014—0.014mol/L。
7、根据权利要求4所述的过渡金属纳米催化剂，其特征在于：所述过渡金属盐选自RuCl3·nH2O、CoCl2·6H2O、NiCl2·6H2O和FeCl3·6H2O中的一种或几种，所述液体介质选自水、醇、烃、醚和离子液体。
8、根据权利要求7所述的过渡金属纳米催化剂，其特征在于：所述液体介质选自水、乙醇、环己烷、1，4-二氧六环或[BMIM][BF4]离子液体。
9、一种进行费托合成反应的方法，是将CO和H2在催化剂作用下进行催化反应，其特征在于：所述催化剂为权利要求1—8任一所述的过渡金属纳米催化剂。
10、根据权利要求9所述的方法，其特征在于：所述催化反应的温度为100—200℃。
11、根据权利要求10所述的方法，其特征在于：所述催化反应的温度为100℃或150℃。
12、根据权利要求9所述的方法，其特征在于：CO和H2的总压力为0.1—10MPa。
13、根据权利要求12所述的方法，其特征在于：CO和H2的总压力为3MPa。
14、根据权利要求9所述的方法，其特征在于：催化反应中，H2/CO的摩尔比为0.5—3∶1。
15、根据权利要求14所述的方法，其特征在于：催化反应中，H2/CO的摩尔比为0.5、1.0或2.0。
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