CN103459355A - 用于将合成气转化为低级烯烃的改进的Fischer-Tropsch法 - Google Patents
用于将合成气转化为低级烯烃的改进的Fischer-Tropsch法 Download PDFInfo
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Abstract
低级烯烃的Fischer-Tropsch合成如下实现：在300℃至最多400℃的温度使用担载的基于铁的催化剂在至少2兆帕的总系统压力下使用至少3∶1的氢气与一氧化碳体积比将合成气进料流转化，具有显著较低的生焦速率，与在小于2兆帕的总系统压力获得的相比。
Description
本申请是非临时申请，要求2011年4月4日提交的题为“FISCHER-TROPSCH PROCESS FOR CONVERTING SYTHESIS GAS TOA LOWER OLEFIN”的美国临时专利申请61/471,330的优先权，将其教导通过参考并入本申请，以下如同全文再现。
本发明总地涉及由包含一氧化碳(CO)和氢气(H2)的进料流通过例如Fischer-Tropsch法使用担载的基于铁的催化剂制备低级烯烃(即包含2至8个碳原子的那些(C2至C8))。本发明特别涉及这样的方法，其包括特定组的工艺参数，该组工艺参数可得到，与使用相同催化剂但是使用不同于上述特定组工艺参数的Fischer-Tropsch工艺参数所得到的相比而言，显著较低水平的碳沉积(也称为“生焦”)。
合成气体或“合成气”通常适用于包含CO和H2的混合物并且可以包括一定量的二氧化碳(CO2)。经Fischer-Tropsch合成法由合成气制备烯烃优选地包括前体步骤，该步骤包括减少或甚至完全除去CO2。
合成气生产经多种方法进行，包括天然气的蒸气转化，煤或生物质的气化，以及废料的燃烧或气化。与非可再生原料例如煤相比，环境考量偏向于使用可再生原料例如生物质或废料。
Fischer-Tropsch合成法(FTS)是催化的化学反应，其中将合成气转化为各种形式的烃，该FTS通常使用基于铁或钴的催化剂，但是也已经可使用镍和钌。FTS涉及多个竞争的化学反应，而非单一反应。
低级烯烃，特别是包含2至8个碳原子的那些(C2至C8)、优选为包含2至6个碳原子的那些(C2至C6)更优选为包含2至4个碳原子的那些(C2至C4)，可作为多种方法的原料广泛用于化学工业，所述方法包括但不限于，合成烯烃均聚物例如聚乙烯和聚丙烯以及多种共聚物(例如线性低密度聚乙烯，乙烯和包含例如4、6或8个碳原子的共聚单体的共聚物，分别为乙烯/丁烯共聚物，乙烯/己烯共聚物，以及已知的乙烯-辛烯共聚物，和丙烯-乙烯无规或嵌段共聚物)和互聚物(该一般性术语有时包括共聚物(两种可聚合单体)，三元共聚物(三种可聚合单体)和四元共聚物(四种可聚合单体)或任何大数目的可共聚单体。
基于铁的催化剂比基于钴的催化剂有利于FTS，因为前者相对于后者提供以下的一种或多种：a)较高收率的低级烯烃，b)较高水平的水煤气变换(WGS)活性，和c)较低的成本。
非均相催化领域的技术人员知道，这样的催化剂包含催化活性部分(针对本发明优选为基于铁的部分)，和催化惰性部分或载体，其中后者占催化剂的主要(大于50%)部分。这区别于非均相催化剂与其中载体占催化剂较小(小于50%)部分的本体催化剂。
共同未决的专利申请P87211PC00公开了制备低级烯烃的方法，如下进行：在高于270摄氏度(℃)、优选为不高于500℃的温度，使用非均相或担载的基于铁的催化剂将包含CO和H2的进料流转化。催化剂包括担载量为至少1重量%(wt%)的分散在对铁化学惰性的载体上的含铁粒子，基于载体的重量。说明性的载体包括二氧化硅，氧化铝，二氧化硅-氧化铝，氧化钛，氧化锆，氧化镁，氧化锰，金属碳化物，金属氮化物，金属硅化物，含碳物质，合成粘土材料，和天然粘土材料，其中优选α-氧化铝，碳纳米纤维，碳化硅或氮化硅。H2和CO存在的摩尔比为：H2:CO为0.1:1至10:1，优选为小于3:1，更优选为小于2:1，最优选为0.5:1至1:1。工艺条件包括：反应温度高于270℃，优选为高于290℃，更优选为高于300℃，最优选为高于310℃，但优选为不高于500℃，更优选为不高于450℃，最优选为不高于400℃。工艺条件也包括：压力为1巴(100千帕(KPa)至700巴(70兆帕(MPa)，优选为5巴(500KPa)至100巴(10MPa)，更优选为10巴(1MPa)至50巴(5MPa)。优选的温度和压力组合为340℃至360℃和15巴(1.5MPa)至25巴(2.5MPa)。
FTS可以在本领域技术人员已知那些中选择的任何适当反应器中进行，其中流化床反应器或多管固定床反应器是优选的。而且，可以使用适用于反应器的任何已知的催化剂装载技术。进一步的信息可以参见Fischer-Tropsch Technology，A.Steynberg and M.Dry(Editors)，Studies in Surface Science andCatalysis152，Chapter2:Fischer-Tropsch Reactors，Elsevier B.V.，Amsterdam(2004)。
Catalysts Science and Technology，J.R.Anderson and M.Boudart(Editors)，Chapter4(M.E.Dry)，pages159-256(1981)讨论了影响催化剂活性损失和碳沉积在铁催化剂上的速率的主要因素。在第195-196页，作者讨论了Fischer-Tropsch催化剂活性的损失的四种机理，其中之一是由于含碳物质的沉积(也称为“淤塞”)导致活性面积损失。在第202页，作者陈述“当碳沉积到铁催化剂上，粒子溶胀并碎裂”。在第206页，作者指出一个发现，即，在碳沉积速率和在反应器入口处CO分压与H2分压之比之间存在关系。在表16下面，作者观察到，当总压增加且H2:CO比率增加时，碳沉积速率下降。
英国专利(GB)1439007部分教导了，在给定的CO分压，可以仅通过增加氢气分压降低碳沉积的速率。专利权人测试了32千克每平方厘米(3.14MPa)至70(6.86MPa)的压力和280℃至450℃、优选为305℃至330℃的温度。在表1中，专利权人指出，当总压和H2:CO比率增加时，碳沉积速率降低。专利权人测试了用钾改性的“纯”铁催化剂，该催化剂有时称为“本体”催化剂，与用于本发明的担载型催化剂相反。在一个实施例中，专利权人报告了2.6克碳每100克铁每100小时的碳沉积速率，这等于6x10-9摩尔碳每克铁每秒。
本领域技术人员理解，非均相催化剂包含两部分，催化活性部分和催化惰性部分(也称为载体)，其中后一部分占催化剂的多于50重量%(wt%)，基于总催化剂重量，通常该重量百分比可高达90wt%。作为对照，在本体催化剂中，催化惰性部分占催化剂的小于50wt%，基于总催化剂重量，通常该重量百分比可为10wt%或更小。本领域技术人员明白，在本体型铁催化剂和担载型铁催化剂之间结构和铁含量方面的差异导致催化剂的生焦性质不同。
在一些方面，本发明是制备低级烯烃的改进方法，如下进行：在大于300℃至最多400℃的温度使用担载的基于铁的催化剂将包含一氧化碳和氢气的进料流转化，所述催化剂包含担载量为基于总催化剂重量至少1wt%的分散在载体上的含铁的粒子，所述载体对铁化学惰性，其中所述改进包括在a)、b)和c)的组合实现转化，其中a)总系统压力为至少20巴(2兆帕)，b)氢气与一氧化碳的体积比为至少3:1，c)氢气分压为至少15巴(1.5兆帕)，由此所述催化剂在四小时生产时间之后的生焦速率小于1x10-7摩尔碳每克催化剂每秒。
在一些方面，改进方法还包括：进料流气时空速为大于15,000hr-1至小于170,000hr-1。
改进方法使用大于300℃至最多400℃、优选为320℃至380℃的温度。
改进方法包括：氢气与一氧化碳的体积比为至少3:1，优选为至少4:1，更优选为至少5:1。
改进方法在四小时生产时间后产生的生焦速率小于1x10-7摩尔碳每克催化剂每秒，优选为小于或等于8.5x10-8摩尔碳每克催化剂每秒，更优选为小于或等于6.0x10-8摩尔碳每克催化剂每秒，仍更优选为小于或等于3.5x10-8摩尔碳每克催化剂每秒，甚至更优选为小于或等于1x10-9摩尔碳每克催化剂每秒。
在以下段落中，阿拉伯数字表示本发明的实施例(Ex)，而大写字母表示对比例(CEx)。
经由水性早期润湿浸渍在环境压力使用包含5.5毫升(mL)去矿物质水和2.94克(g)柠檬酸铵铁(III)(绿色粉末，14.5-16重量%(wt%)Fe)和4gα-Al2O3(BASF Nederland BV，筛选部分为0.212毫米(mm)至0.425mm，BET表面积为8.1平方米每克(m2/g)，和孔体积为0.5立方厘米每克(cm3/g))的溶液制备α-氧化铝(α-Al2O3)担载的铁(Fe)催化剂。在每个浸渍步骤之后，在环境温度(标称为25℃)和60毫巴(mbar)(6KPa)的压力将催化剂干燥2小时。可替换地，在每个浸渍步骤之后，在120℃在静态空气中在大气压干燥催化剂。在通过连续的浸渍-干燥循环将所有的溶液混入载体之后，在流动的空气下在90℃将浸渍的α-Al2O3干燥1小时，然后将其在500℃煅烧2小时，以5℃/分钟的速率从90℃升温至500℃，然后停止加热并使其冷却至环境温度。
煅烧的物料具有的氧化铁(Fe2O3)晶体尺寸为25纳米(基于X-射线粉末衍射(XRD)使用CoKα辐射源和在38.9°的2-θ角测得的Fe2O3峰)，表面积为15m2/g。基于X-射线荧光光谱法(XRF)，煅烧的物料包含84.8wt%的α-Al2O3，14.1wt%的Fe2O3(9.9wt%Fe)，0.48wt%的钠(Na)，0.071wt%的硫(S)，组合物的剩余物由痕量的硅、钙、铬和锰的氧化物组成，各wt%均基于总的煅烧物料重量。
将煅烧物料在350℃使用20体积%(vol%)H2和80vol%氩气的混合物还原3.2小时，各vol%均基于总混合物体积，所述混合物以140升每克催化剂每小时(L·gcat -1·h-1)的空速流动。
使一部分催化剂经受以下表1中所示的FTS条件，其中pH2和pCO分别表示进料流中的氢气分压和一氧化碳分压。结果总结于以下表2，其中“HC”表示烃，“WTY”表示重时收率，以10-6摩尔转化为烃(C1-C8)的CO每克催化剂每秒(10-6·molCO·gcat -1·s-1)为单位表示，生焦速率以10-6摩尔形成的碳每克催化剂每秒(10-6·molC·gcat -1·s-1)为单位表示，C2-C4表示两个碳原子至四个碳原子，C5-C8表示五个碳原子至八个碳原子。所有的选择性值均按照重量百分比(wt%)表示，基于C1-C8烃产物的分析，并且标准化为产物流中C1-C8烃产物(具有一个碳原子到至多八个碳原子的碳产物，不包括CO2)的重量，基于不含二氧化碳的产物。
表1
表2.在表1中提及的各Fischer Tropsch条件的结果的总结
表2中的数据表明使用20巴(2MPa)的总压和至少3:1的H2/CO比率，极低的生焦速率(小于1x10-7molC·gcat -1·s-1，在几种情况下小于1x10-9molC·gcat -1·s-1)在表1所示的温度和空速是明显的。作为对比，甚至在相似的空速，甚至在相同H2/CO体积比(例如在CEx C中为5)时总压的降低(例如在CEx A-C中降至10巴/1MPa)得到显著较高的生焦速率(CEx C的生焦速率为3.98x10-7molC·gcat -1·s-1，相比于Ex1的在相似空速和相同温度生焦速率小于1x10-9molC·gcat -1·s-1)。Ex1(空速为84000h-1)与Ex4(空速为17000h-1)的比较表明，在所有其它条件均相同或几乎相同的情况下，在两种完全相异的空速下得到小于1x10-9molC·gcat -1·s-1的生焦速率，但是本领域技术人员认为当空速增加时生焦速率倾向于增加。表2中的催化剂性能数据表明，Ex1至7的催化剂在WTY和对所需产物(即乙烯和丙烯)的选择性方面显示了活性。
Claims (9)
1.通过在大于300℃至最多400℃的温度使用担载的基于铁的催化剂将包含一氧化碳和氢气的进料流转化而制备低级烯烃的改进方法，所述催化剂包含担载量为基于总催化剂重量至少1wt%的分散在载体上的含铁的粒子，所述载体对铁化学惰性，其中所述改进包括在a)、b)和c)的组合实现所述转化，其中a)为总系统压力为至少20巴(2兆帕)，b)为氢气与一氧化碳的体积比为至少3:1，c)为氢气分压为至少15巴(1.5兆帕)，由此所述催化剂在四小时生产时间之后的生焦速率小于1x10-7摩尔碳每克催化剂每秒。
2.权利要求1的改进方法，其中所述组合进一步包括：进料流气时空速为大于15,000hr-1至小于170,000hr-1。
3.权利要求1或权利要求2的改进方法，其中所述温度为320℃至380℃。
4.权利要求1至3中任一项的改进方法，其中氢气与一氧化碳的体积比为至少4:1。
5.权利要求1至3中任一项的改进方法，其中氢气与一氧化碳的体积比为至少5:1。
6.权利要求1至5中任一项的改进方法，其中在四小时生产时间之后的生焦速率小于或等于8.5x10-8摩尔碳每克催化剂每秒。
7.权利要求1至6中任一项的改进方法，其中在四小时生产时间之后的生焦速率小于或等于6.0x10-8摩尔碳每克催化剂每秒。
8.权利要求1至5中任一项的改进方法，其中在四小时生产时间之后的生焦速率小于或等于3.5x10-8摩尔碳每克催化剂每秒。
9.权利要求1至5中任一项的改进方法，其中在四小时生产时间之后的生焦速率小于或等于1.0x10-9摩尔碳每克催化剂每秒。
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2012138415A1 (en) | 2012-10-11 |
| BR112013025087A2 (pt) | 2017-02-14 |
| EP2694457A1 (en) | 2014-02-12 |
| EP2694457B1 (en) | 2019-06-19 |
| US20140024727A1 (en) | 2014-01-23 |
| US9126876B2 (en) | 2015-09-08 |
| CN103459355B (zh) | 2016-06-29 |
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