CN1326975C - 使用费－托催化剂和含沸石催化剂的费－托法 - Google Patents
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Abstract
本发明涉及将一氧化碳和氢气转化为C5 +烃类混合物的费-托法，在该方法中采用了费-托催化剂颗粒和流化床催化裂化(FCC)催化剂颗粒。该FCC催化剂可以是新鲜的FCC催化剂，或者是平衡催化剂(E-cat)。
Description
本发明涉及采用费-托催化剂和含沸石催化剂将一氧化碳和氢气转化为C5 +烃类混合物的费-托法。
费-托法通常包括下列工艺步骤。第一步涉及使碳源(例如煤或天然气)和氧源(例如水蒸气、空气或氧气)发生反应以形成一氧化碳和氢气的混合物，该混合物通常称为合成气。第二步涉及使一氧化碳和氢气与费-托催化剂接触产生烃类和水。根据工艺条件和采用的催化剂，烃类的性质和链长度会不同。费-托反应的主要产物是直链烯烃和链烷烃和水，但也可发生有限的异构化和杂原子如氧的引入。该第二步通常采用的催化剂为含铁和/或含钴的催化剂。为了在该第二步中加强异构化，可以加入助催化剂。第三步涉及对第二步中生成的烃类进行异构化以生产更有价值的产品。例如可以裂解产物中的长链成分以形成柴油或汽油范围的产品，并且可以对直链链烷烃进行异构化以改进柴油产品的性能如浊点和倾点。一般来讲，对于该第三步采用适应的加氢处理催化剂。
US5928980公开了在费-托法的第二步中使用第VIII族金属，优选钴和/或铁浸渍过的用过的流化床催化裂化(FCC)催化剂。这个催化剂组合物通过采用金属盐浸渍该用过的FCC催化剂、焙烧浸渍的FCC催化剂以得到负载的金属氧化物并且在还原性气体气氛中将金属氧化物还原成金属而制备。该浸渍的金属用作费-托催化剂。
该现有技术催化剂组合物的制备要求麻烦的工艺，涉及浸渍、焙烧和还原步骤。因此本发明的目的是提供一种采用更易制备的费-托催化剂和FCC催化剂体系将一氧化碳和氢气转化为C5 +烃类混合物的方法。第二个目的是提供一种采用根据需要能更灵活使用的催化剂体系的方法。第三个目的是提供便宜的催化剂体系。
现有技术仅公开了在费-托法中采用用过的FCC催化剂。本发明的第四个目的是通过还使用其它类型的FCC催化剂扩大用于费-托法中的FCC催化剂的范围。
本发明的方法采用费-托催化剂颗粒和流化床催化裂化催化剂颗粒。因此，本发明的催化剂组合物可以通过简单混合现有的费-托催化剂颗粒和FCC催化剂颗粒而制备。其制备不要求工业上不可取的浸渍步骤。
在一个实施方案中，费-托催化剂颗粒和FCC催化剂颗粒可以其中包埋有这两种颗粒的成型体形式使用。成型体的例子有喷雾干燥的颗粒(微球)、挤出物、丸、球等。
该成型体可以通过对费-托催化剂颗粒和FCC催化剂颗粒的物理混合物进行成型处理而制备。制得该成型体的合适方法包括喷雾干燥、造粒、挤出(任选结合捏合)、造珠或在催化剂和吸收剂领域领域中使用的任何其它传统成型方法或其结合。例如，如果费-托催化剂颗粒的制备涉及喷雾干燥步骤，可以在喷雾干燥前将FCC催化剂加入费-托催化剂中，并随后喷雾干燥所得混合物。
如果需要，可加入基体或粘合材料以改进成型体的机械强度。合适的基体或粘合材料的例子有氧化铝、二氧化硅、粘土和其混合物。通常优选包含氧化铝的基体或粘合材料。优选基体或粘合材料(如果存在的话)的存在量为10-40wt％，更优选15-35wt％，最优选25-35wt％，基于催化剂组合物的总重量。
术语“FCC催化剂”包括新鲜的FCC催化剂、用过的FCC催化剂和平衡催化剂(E-cat)。用过的FCC催化剂比新鲜的FCC催化剂更便宜。此外，其使用导致对废弃材料的再利用，这在经济和环境上是有利的。
如果FCC催化剂颗粒和费-托催化剂颗粒不是以其中包埋有这两种颗粒的成型体的形式，那么费-托催化剂颗粒和FCC催化剂颗粒可以根据需要单独计量加入费-托单元。这产生了很大的灵活性。例如，如果在处理过程中工艺条件发生改变，或者如果其中一种催化剂比另一种更快失活，那么其中一种催化剂可以采用比另一种催化剂更快的计量加入速率加入。而且，E-cat或用过的FCC催化剂的质量每批都不同，这种不同可以通过调节FCC催化剂颗粒相对于费-托催化剂颗粒的计量加入速率而得到补偿。此外，可以在费-托法的第二步中使用两种类型的催化剂颗粒，或者在第二步中使用费-托催化剂颗粒而在第三步中使用FCC催化剂颗粒。
术语“FCC催化剂”指适合用于FCC方法的任何催化剂组合物。尽管优选含Y沸石的FCC催化剂，但任何传统的FCC催化剂都可用于本发明的方法中。该FCC催化剂通常含有Y沸石、粘土(如高岭土、变高岭石、膨润土)、二氧化硅、氧化铝、稀土金属化合物等。合适金属的例子有稀土金属如Ce、La，和元素周期表中第IV-VIII族的过渡金属如V、Cr、Mn、Fe、Co、Ni、Cu、Zr、Nb、Ru、Re等。金属化合物可用于例如增加颗粒的强度(如La化合物)、增强催化剂的稳定性(如Ni化合物)或增强CO的转化率(如Fe、Co或Ru化合物)。金属化合物优选以0.1-10wt％，更优选0.3-2wt％的用量(按照氧化物计算，并且基于含金属FCC催化剂的总重量)存在于FCC催化剂颗粒中或FCC催化剂颗粒上。可以以本领域中已知的任何方式将金属化合物沉积到FCC催化剂颗粒上。该方法的例子有浸渍、离子交换以及可溶金属盐的沉积沉淀。如果需要，在金属化合物沉积下来以后，对金属沉积的FCC催化剂颗粒进行焙烧和/或预还原。
相比于新鲜的FCC催化剂采用用过的FCC催化剂的另一个优势在于用过的FCC催化剂通常含有所需的金属化合物，因为将要在FCC单元中进行裂解的烃类进料通常含有各种金属如镍和钒。因此，不需要另外的沉积步骤以引入该金属化合物。
费-托催化剂可以是任何传统的费-托催化剂，优选包含铁和/或钴。对于这些催化剂的制备可参考如WO01/97968、WO01/89686和WO01/70394。费-托催化剂可以采用各种金属如Al、Ti、Cr、Mn、Ca、Na和/或K促进。此外，费-托催化剂颗粒可含有粘合材料如二氧化硅和/或氧化铝。
FCC催化剂颗粒和费-托催化剂颗粒两者都可用于费-托法的第二步中，或者以各自的颗粒的形式，或者以其中包埋这两种颗粒的成型体形式。基于FCC催化剂颗粒和费-托催化剂颗粒的总重量，优选FCC催化剂颗粒用量为5-40wt％，更优选10-30wt％。
第二步可以在任何合适的反应器中进行，如(固定)流化床反应器。温度范围优选250-400℃，更优选300-370℃，最优选330-350℃。压力范围优选10-60巴，更优选15-30巴，最优选约20巴。优选H2/CO体积比的范围为0.2-6.0，更优选0.5-6，最优选1-3。
第三步通常在150-600℃的温度下进行，更优选200-500℃，最优选300-400℃。优选压力范围为5-60巴，更优选15-40巴，最优选20-30巴。
所得烃类产物按质量含量计算优选含有至少35％，更优选至少45％，最优选至少50％的C5 +化合物。该方法可用于生产支链烃类、烯烃和/或芳香族化合物。优选该方法用于生产液体燃料，特别是柴油和汽油，优选无铅汽油。
实施例
下列试验说明在典型的费-托工艺条件下以Y沸石为基础的FCC催化剂(新鲜的和E-cat)对直链烯烃产物异构化的适用性。适用于此目的的催化剂可以在费-托法的第二步(作为助催化剂)或者第三步中使用以加强直链烯烃产物的异构化。
为此，测试了FCC催化剂对1-己烯的氢化异构反应的性能。进行性能测试的反应条件(温度、总压和二氢压力(dihydrogen pressure))等同于典型高温费-托法中存在的条件：
温度：340℃
总压：20巴
催化剂输入量：2.2g
WHSV，1-己烯：2.85g/g/hr(基于存在的沸石量)
H2分压：9巴
N2分压：10.8巴
1-己烯分压：0.22巴
H2/1-己烯的摩尔比：40.9
N2/1-己烯的摩尔比：49.1
FCC催化剂在反应器中在20巴的氢气压力和340℃下就地还原1小时。在还原步骤完成后，引入氮气流，并且随后计量加入1-己烯(0.11ml/min)。反应产物的组成通过在线GC分析跟踪。
按照该程序测试了三种不同类型的FCC催化剂：含有少量稀土(RE)金属的新鲜FCC催化剂、含有多量稀土金属的新鲜FCC催化剂 和从含有少量RE的FCC催化剂得来的平衡FCC催化剂(E-cat)。在0.5小时和17.5小时的运转时间时在这些测试中测得的产物分布分别列于表1和2中。
在这些表中，n-C6表示正构C6链烷烃，i-C6表示支链C6链烷烃，n-C6＝表示正构C6烯烃，i-C6＝表示支链C6烯烃，而＜C6和＞C6分别表示具有少于和多于6个碳原子的化合物。
表1-在0.5小时运转时间时的测试结果
| 新鲜FCC少量RE | 新鲜FCC多量RE | E-cat | |
| l-己烯的转化率，wt％n-C6，wt％i-C6，wt％n-C6＝，wt％i-C6＝，wt％＜C6，wt％＞C6，wt％i-C6+i-C6＝，wt％ | 93.819.819.29.432.810.98.252.0 | 99.428.541.60.73.220.26.044.8 | 94.029.613.724.324.54.43.738.2 |
表2-在17.5小时运转时间时的测试结果
| 新鲜FCC少量RE | 新鲜FCC多量RE | E-cat | |
| 1-己烯的转化率，wt％n-C6，wt％i-C6，wt％n-C6＝，wt％i-C6＝，wt％＜C6，wt％＞C6，wt％i-C6+i-C6＝，wt％ | 90.810.012.820.247.33.46.560.1 | 91.411.014.915.145.65.38.460.5 | 91.815.59.339.330.63.02.739.9 |
由这些表可以看出，具有少量RE的新鲜FCC催化剂对支链C6烯烃(i-C6＝)和支链C6链烷烃(i-C6)具有高选择性。在0.5小时和17.5小时运转时间时异构化产物的总量分别为52.0wt％和60.1wt％。高的异构化选择性伴随着低水平的裂解：在17.5小时运转时间时只得到3.4wt％的C6以下产物(＜C6)。在整个运行过程中芳香族产物的量远远低于1wt％。
具有多量RE的新鲜FCC催化剂对支链C6烯烃(i-C6＝)和支链C6链烷烃(i-C6)也显示出高选择性。在0.5小时和17.5小时运转时间时异构化产物的总量分别为44.8wt％和60.5wt％。在17.5小时运转时间时的裂解水平为5.3wt％。在整个运行过程中芳香族产物的量都远远低于1wt％。
平衡FCC催化剂对支链C6烯烃(i-C6＝)和支链C6链烷烃(i-C6)显示出比新鲜FCC催化剂稍低的选择性。在0.5小时和17.5小时运转时间时异构化产物的总量分别为38.2wt％和39.8wt％。在17.5小时运转时间时的裂解水平仅为3.0wt％。再有，在整个运行过程中芳香族产物的量都远远低于1wt％。虽然此E-cat的异构化水平低于新鲜FCC催化剂，但用于费-托产品仍然可以接受，特别是在第二步中用作助催化剂。
这些实验显示FCC催化剂能够在典型的费-托条件下异构化直链烯烃。这表明它们适合用于费-托法的第二步和第三步中。
Claims (11)
1.一种将一氧化碳和氢气转化为C5 +烃类混合物的费-托法，包括将碳和氢气与包含费-托催化剂颗粒和含Y沸石的流化床催化裂化催化剂颗粒的催化剂接触。
2.如权利要求1所述的方法，其中一氧化碳和氢气的反应混合物与费-托催化剂颗粒和流化床催化裂化催化剂颗粒接触。
3.如权利要求2所述的方法，其中费-托催化剂颗粒和流化床催化裂化催化剂颗粒独立地计量加入反应混合物中。
4.如权利要求3所述的方法，其中费-托催化剂颗粒和流化床催化裂化催化剂颗粒以不同的速率计量加入。
5.如权利要求2所述的方法，其中费-托催化剂颗粒和流化床催化裂化催化剂颗粒以其中包埋有这两种颗粒的成型体形式使用。
6.如权利要求1所述的方法，其中碳和氢气首先与费-托催化剂颗粒接触，随后与流化床催化裂化催化剂颗粒接触。
7.如前述任意一项权利要求所述的方法，其中费-托催化剂颗粒包含铁。
8.如前述任意一项权利要求所述的方法，其中费-托催化剂颗粒包含钴。
9.如前述任意一项权利要求所述的方法，其中流化床催化裂化催化剂是用过的流化床催化裂化催化剂。
10.如权利要求1-8所述的方法，其中流化床催化裂化催化剂是平衡流化床催化裂化催化剂。
11.如前述任意一项权利要求所述的方法，其中在所述流化床催化裂化催化剂上已沉积一种金属化合物。
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| BRPI0705939A2 (pt) * | 2007-10-29 | 2009-06-23 | Petroleo Brasileiro Sa | processo para a produção de catalisadores hìbridos para a sìntese de fischer-tropsch e catalisador hìbrido produzido de acordo com o processo |
| BRPI0704436A2 (pt) * | 2007-11-30 | 2009-07-28 | Petroleo Brasileiro Sa | processo de produção de hidrocarbonetos |
| US20100160464A1 (en) * | 2008-12-24 | 2010-06-24 | Chevron U.S.A. Inc. | Zeolite Supported Cobalt Hybrid Fischer-Tropsch Catalyst |
| WO2010078371A2 (en) * | 2008-12-29 | 2010-07-08 | Chevron U.S.A. Inc. | Preparation of cobalt-containing acidic support-based fischer-tropsch catalysts |
| WO2010078360A2 (en) * | 2008-12-29 | 2010-07-08 | Chevron U.S.A. Inc. | Preparation of cobalt-containing fischer-tropsch catalysts |
| US20100312030A1 (en) * | 2009-06-04 | 2010-12-09 | Chevron U.S.A., Inc. | Process of synthesis gas conversion to liquid fuels using synthesis gas conversion catalyst and noble metal-promoted acidic zeolite hydrocracking-hydroisomerization catalyst |
| US7825164B1 (en) * | 2009-11-18 | 2010-11-02 | Chevron U.S.A. Inc. | Process of synthesis gas conversion to liquid fuels using mixture of synthesis gas conversion catalyst and dual functionality catalyst |
| US7943674B1 (en) | 2009-11-20 | 2011-05-17 | Chevron U.S.A. Inc. | Zeolite supported cobalt hybrid fischer-tropsch catalyst |
| US20110160315A1 (en) * | 2009-12-30 | 2011-06-30 | Chevron U.S.A. Inc. | Process of synthesis gas conversion to liquid hydrocarbon mixtures using synthesis gas conversion catalyst and hydroisomerization catalyst |
| US8519011B2 (en) | 2010-10-28 | 2013-08-27 | Chevron U.S.A. Inc. | Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst, hydrocracking and hydroisomerization catalyst |
| US8481601B2 (en) | 2010-11-23 | 2013-07-09 | Chevron U.S.A. Inc. | Process of synthesis gas conversion to liquid hydrocarbon mixtures using a catalyst system containing ruthenium and an acidic component |
| US8445550B2 (en) | 2010-11-23 | 2013-05-21 | Chevron U.S.A. Inc. | Ruthenium hybrid fischer-tropsch catalyst, and methods for preparation and use thereof |
| US20130158138A1 (en) * | 2011-12-15 | 2013-06-20 | Chevron U.S.A. Inc. | Integral synthesis gas conversion catalyst extrudates and methods for preparing and using same |
| US9878314B2 (en) | 2013-11-26 | 2018-01-30 | Infra XTL Technology Ltd. | Catalyst for direct production of isoparaffins-rich synthetic oil and a method for preparing the catalyst |
| US9290700B2 (en) | 2014-08-11 | 2016-03-22 | Infra XTL Technology Limited | Method for preparing synthetic liquid hydrocarbons from CO and H2 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4906671A (en) * | 1985-08-29 | 1990-03-06 | Mobil Oil Corporation | Fischer-tropsch process |
| CN1354779A (zh) * | 1999-04-06 | 2002-06-19 | 沙索尔技术股份有限公司 | 生产合成石脑油燃料的方法及用该方法生产的合成石脑油燃料 |
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| US3254023A (en) | 1964-06-08 | 1966-05-31 | Socony Mobil Oil Co Inc | Method of heat balancing in organic catalytic reactions |
| US4269783A (en) | 1977-03-07 | 1981-05-26 | Mobil Oil Corporation | Conversion of syngas to high octane olefinic naphtha |
| US4652538A (en) | 1983-11-01 | 1987-03-24 | Union Carbide Corporation | Catalysts for conversion of syngas to liquid motor fuels |
| US4595702A (en) | 1984-01-20 | 1986-06-17 | Mobil Oil Corporation | Conversion of synthesis gas to liquid hydrocarbons |
| US4556645A (en) | 1984-06-27 | 1985-12-03 | Union Carbide Corporation | Enhanced catalyst for conversion of syngas to liquid motor fuels |
| US4665042A (en) * | 1985-05-14 | 1987-05-12 | The Standard Oil Company | Catalysts for the conversion of syn gas |
| US5928980A (en) | 1997-02-06 | 1999-07-27 | Research Triangle Institute | Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1354779A (zh) * | 1999-04-06 | 2002-06-19 | 沙索尔技术股份有限公司 | 生产合成石脑油燃料的方法及用该方法生产的合成石脑油燃料 |
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