CN103521249A - 一种用于合成气转化的磷化物催化剂和制备方法及其应用 - Google Patents
一种用于合成气转化的磷化物催化剂和制备方法及其应用 Download PDFInfo
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- CN103521249A CN103521249A CN201210231677.7A CN201210231677A CN103521249A CN 103521249 A CN103521249 A CN 103521249A CN 201210231677 A CN201210231677 A CN 201210231677A CN 103521249 A CN103521249 A CN 103521249A
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- phosphide
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
本发明提供一种用于合成气转化的磷化物催化剂和制备方法及其应用,具体地提供一种用于以合成气为原料合成含氧化合物的含有金属态Fe、Co和Ni中的一种或多种及其磷化物的催化剂和制备方法及其应用。根据本发明,提供在一定温度和压力反应条件下,将H2/CO转化为烃类和含氧化物的具有由SiO2或Al2O3负载的Fe、Co和Ni中的一种或多种及其磷化物的催化剂。催化剂由活性组分和载体两部分组成。活性组分为由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物。载体选用SiO2或者Al2O3。在固定床或浆态床反应器中,在一定的温度和压力以及在本发明催化剂的作用下,H2/CO可高活性、高选择性地转化为两个碳及其以上的含氧化物和烃类。
Description
技术领域
本发明涉及一种用于以合成气原料转化为烃类和含氧化物的SiO2或Al2O3负载的由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂和制备方法及其应用,详细地涉及在一定温度和压力下,以CO、H2混合气为原料高效制取两个碳及其以上的含氧化物的SiO2或Al2O3负载的由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂和制备方法及其应用。
技术背景
中国作为世界最大的产煤国,从资源利用和环境保护的角度看,利用高效洁净煤炭资源技术,开发“绿色燃料”具有重要的战略意义和应用前景。
CO催化加氢合成烃类及含氧化物是煤炭资源洁净利用的重要途径之一。近年来,低碳混合醇在燃料和化工领域的应用价值逐步凸现,相关研究日益活跃。
用于低碳混合醇合成的均相催化剂大致可分为贵金属和非贵金属两类,其中贵金属Rh催化剂可以转化合成气为乙醇和其它两个碳及其以上含氧化物,然而,由于Rh金属供应有限,成本高.因而商业应用上规模有限。另一方面,从合成气制低碳混合醇的主要非贵金属催化剂有改性的甲醇合成催化剂,改性的Fischer-Tropsch(F-T)合成催化剂和碱金属掺杂的Mo催化剂。它们中,具有工业应用前景的代表性催化剂体系分为以下4种:
(1)Dow化学公司开发的MoS催化剂体系(Sygmol工艺);
(2)法国石油研究所开发的Cu-Co催化剂体系(IFP工艺);
(3)Lurgi公司开发的Cu-Zn-Al催化剂体系(Octamix工艺);和
(4)Sham公司开发的Zn-Cr-K催化体系(MAS工艺)。
以上4种催化剂体系各有其特色。但是,总体看来,所开发的催化剂体存在活性、选择性、稳定性及经济性等方面的不足,开发高活性和高两个碳及其以上含氧化物选择性的催化剂依然是研究的难点和关键。尽管研究者对于这些催化剂体系的开发已做出了很大的努力,但还有很大空间来提高催化活性和高级醇的选择性。
过渡金属磷化物作为一种重要的加氢催化剂在许多涉氢反应中表现出了类贵金属性质,具有潜在的代替贵金属催化剂的可能性。Kevin J.Smith等(Appl.Catal.,A2010,378,59-68,Catal.Today 2011,171,266-274)研究了磷化钼催化剂在CO加氢反应的应用,其结果表明产物明显不同与传统的非贵金属催化剂。两个碳及其以上含氧化物产物在液相产物中的含量达到76%(C%)。
发明内容
本发明的一个目的在于提供一种用于以合成气为原料转化为烃类和含氧化物的SiO2或Al2O3负载的由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂,所述催化剂的制备方法及在合成气为原料转化为烃类和含氧化物的反应中的应用。与现有的技术相比,本发明的催化剂不采用Rh等贵金属,同时实现较高的两个碳及其以上含氧化物的活性和选择性。
为实现上述目的,本发明在一个方面提供一种负载型催化剂,所述负载型催化剂用于将合成气原料转化为烃类和含氧化物,其中:所述负载型催化剂包括活性组分和载体两部分;所述活性组分为由过渡金属及所述过渡金属的磷化物组成的混合物,其中所述过渡金属是Fe、Co和Ni中的一种或多种,其中所述活性组分的重量百分比按金属计为催化剂重量的0.5~30.0%,其中在所述活性成分中,过渡金属原子的摩尔数与磷原子的摩尔数之比在1~10的范围内;并且所述载体为SiO2或Al2O3;其中SiO2的比表面积为100~600m2/g,并且平均孔径为5~90nm;并且Al2O3的比表面积为100~400m2/g,并且平均孔径为4~90nm。
在本发明的一个优选的实施方案中,所述活性组分重量百分比按金属计为催化剂重量的1.0~25.0%。
在本发明的另一个优选的实施方案中,SiO2比表面积为200~400m2/g,并且平均孔径为10~50nm。
在本发明的另一个优选的实施方案中,Al2O3的比表面积为150~300m2/g,并且平均孔径为10~50nm。
在本发明的另一个特别优选的实施方案中,所述负载型催化剂由活性组分和载体两部分组成。
本发明在另一个方面提供一种用于制备烃类和含氧化物的方法,所述方法包括:在反应器中,在上面所述的催化剂存在下,使合成气原料转化为烃类和含氧化物。
在本发明的一个优选的实施方案中,所述反应器为固定床或浆态床反应器。
在本发明的另一个优选的实施方案中,所述方法在100~400℃的温度,1.0~10.0MPa(表压)的反应压力,合成气中的CO/H2按摩尔比计为0.5/1至10/1且空速为100~10000h-1的条件下进行。
本发明在再一个方面提供一种用于制备上面所述催化剂的方法,所述方法包括:将所述活性组分经由浸渍法或沉淀法中的一种或两种负载在所述载体上,然后高温空气中焙烧。
在本发明的一个优选的实施方案中,所述方法还包括将焙烧后的催化剂在H2流中程序升温还原。
具体实施方式
下面详细阐述本发明的内容。
本发明提供一种用于以合成气为原料转化为烃类和含氧化物的催化剂,由活性组分和载体两部分组成,活性组分的重量百分比为0.5~30.0%。活性组分为由过渡金属及所述过渡金属的磷化物组成的混合物,其中所述过渡金属是Fe、Co和Ni中的一种或多种,其中所述活性组分的重量百分比按金属计为催化剂重量的0.5~30.0%,其中在所述活性成分中,过渡金属原子的摩尔数与磷原子的摩尔数之比在1~10的范围内;载体为SiO2或Al2O3;载体中SiO2比表面积为100~600m2/g,平均孔径为5~90nm;并且载体中Al2O3的比表面积为100~400m2/g,平均孔径为4~90nm。
Fe,Ni和Co过渡金属的磷化物具有类贵金属的催化性质,在CO吸附和加氢反应中表现出类贵金属的性能。一般来说,金属态的Fe,Ni和Co催化剂具有CO加氢生成烃类的催化性能,很少生成含氧化物。而且,该金属态的催化剂CO加氢反应中具有碳链增长的特性。而上述的Fe,Ni和Co过渡金属的磷化物往往具有吸附活化CO的性能。因此,可以预测此类催化剂将具有CO加氢生成两个碳及其以上含氧化物的可能性。采用高比表面的氧化物载体可以提高负载金属的分散度,从而提高Fe,Ni和Co过渡金属的利用率。同时,高分散的金属往往易于上述金属磷化物的形成。Al2O3和SiO2是常用的制备负载型催化剂的载体。
本发明的催化剂是用于在一定温度和压力下,CO、H2混合气为原料高效制取两个碳及其以上含氧化物反应。催化剂由活性组分和载体两部分组成。活性组分为由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂。载体选用SiO2或Al2O3等。在固定床或浆态床反应器中以CO/H2为反应原料,在本催化剂作用下,发生CO加氢反应,可高活性和高选择性地转化为两个碳及其以上含氧化物。
含氧化物可以包括甲醇和两个碳及其以上含氧化物。两个碳及其以上含氧化物的实例可以包括:乙醇和乙醛,丙醇和丙醛,丁醇和戊醇等。
烃类可以包括:烷烃如甲烷,乙烷,丙烷,和丁烷,以及烯烃,如乙烯,丙烯和丁烯等。
在本发明的催化剂存在下,CO、H2混合气为原料高效制取两个碳及其以上含氧化物反应的主要产物可以包括:乙醇和乙醛,丙醇和丙醛,丁醇和戊醇等。
本文中所述的低碳是指五个碳原子以下。如低碳混合醇是指五个碳原子以下的混合醇。
在所述“由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物”是指所述的混合物可以由Fe、Co和Ni中的任何一种及其磷化物组成,可以由Fe、Co和Ni中的任意两种及其磷化物组成,也可以由Fe、Co和Ni中的三种及其磷化物组成。
在所述的混合物由Fe、Co和Ni中的任何一种及其磷化物组成的情况下,混合物的实例可以包括:由Fe及其磷化物组成的混合物、由Co及其磷化物组成的混合物、和由Ni及其磷化物组成的混合物。
在所述的混合物由Fe、Co和Ni中的任何两种及其磷化物组成的情况下,混合物的实例可以包括:由Fe和Co及它们的磷化物组成的混合物、由Fe和Ni及它们的磷化物组成的混合物、和由Co和Ni及它们的磷化物组成的混合物。
本发明的反应体系中,可以直接将CO/H2/通入到装有本发明的颗粒状催化剂的固定床或浆态床反应器中,进行CO加氢反应。
本发明的催化剂,过渡金属较佳重量百分含量为0.5~30.0%%,最佳重量含量为1.0~25.0%;载体可选用SiO2的比表面积较佳为100~600m2/g,平均孔径为5~90nm,最佳的比表面积为200~400m2/g,平均孔径最佳为10~50nm;载体也可以采用Al2O3,Al2O3的较佳比表面积为100~400m2/g,平均孔径为4~90nm最佳的比表面积为150~300m2/g,最佳孔径为10~50nm。
本发明的催化剂制备方法可以包括以下步骤:采用SiO2或Al2O3为载体,金属硝酸盐和磷酸氢铵为金属和磷源,配制成水溶液,采用浸渍法浸渍在载体上或沉淀法沉积在载体表面上,干燥,烘干,高温焙烧,即得该催化剂的氧化态前驱物。在H2流中程序升温还原后即得由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂。
在本发明中,催化剂的氧化态前驱物经由H2流中程序升温还原后,在由金属态的Fe、Co和Ni中的一种或多种及其磷化物组成的混合物催化剂中,金属按摩尔计的量与磷化物按磷的摩尔计的量之比在1~10的范围内。
在由金属原子Fe、Co和Ni中的任何一种的磷化物中,金属原子形成三棱柱结构的最小结构单元,这些三棱柱单元以不同的结合方式形成不同的晶格类型,而P原子占据三棱柱内部的空隙。由于P原子的插入,母体金属的体相性质发生了变化。这主要是由于配体效应和电子效应相互作用的结果。一方面电子可以在金属与配体间转移,另一方面由于配体的插入,金属原子在表面上暴露的数目减少,使得与母体金属相比该类化合物的电子构型和晶格构型都发生了显著的变化。在这些不同晶型的晶体中,受P的影响,金属的电子结构和吸附性质都发生了显著的变化,从而导致了催化性能的差异。
每种催化剂的氧化态前驱物使用前,在固定床反应器中H2(GHSV=1000~10000h-1)流中进行原位还原活化,条件为:常压,1~10℃/min从室温升温至300~400℃,0.5~3℃/min从300~400℃升温至500~700℃保持1~6小时在H2流中降温至反应温度,得到所述的催化剂。
本发明中CO、H2混合气为原料高效制取两个碳及其以上含氧化物反应的反应温度为约280℃,反应压力为约5.0MPa,CO/H2=约2/1(摩尔比),空速为约5000h-1。
下面通过具体实施例对本发明做进一步说明。除非另外具体指出,本申请中所述的比例、份数和百分比基于重量。
在实施例中使用的材料如下:
硝酸铁(Fe(NO3)3·9H2O):天津科密欧化学试剂开发中心,分析纯
硝酸钴(Co(NO3)2·6H2O):天津科密欧化学试剂开发中心,分析纯
硝酸镍(Ni(NO3)2·6H2O)天津科密欧化学试剂开发中心,分析纯
磷酸氢二铵((NH4)2HPO3):沈阳联邦试剂厂,分析纯
氧化硅(SiO2):青岛海洋化工,d粒径=0.50mm,球形颗粒,S比表面积=350m2/g,d孔径=15.1nm
氧化铝(Al2O3):山东淄博贝尔化工科技有限公司,d粒径=0.50mm,球形颗粒,S比表面积=150m2/g,d孔径=12.1nm
采用X-射线衍射荧光光谱分析方法(XRF),对实施例中制备出的催化剂中成分的进行半定量测定。
实施例1
实施例1的催化剂为FeP/SiO2(Fe/P=8摩尔比)。称取10.0克SiO2(20~40目),配置8ml含7.21克Co(NO3)2.6H2O和0.29克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例2
实施例2的催化剂为FeP/SiO2(Fe/P=4摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.58克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例3
实施例3的催化剂为FeP/SiO2(Fe/P=2摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和1.17克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例4
实施例4的催化剂为CoP/SiO2(Co/P=8摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.29克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例5
实施例5的催化剂为CoP/SiO2(Co/P=4摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.58克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例6
实施例6的催化剂为CoP/SiO2(Co/P=2摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和1.17克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例7
实施例7的催化剂为NiP/SiO2(Ni/P=8摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.29克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例8
实施例8的催化剂为NiP/SiO2(Ni/P=4摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.58克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例9
实施例9的催化剂为NiP/SiO2(Ni/P=2摩尔比)。称取10.0克SiO2(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和1.17克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述SiO2载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例10
实施例10的催化剂为CoP/Al2O3(Co/P=4摩尔比)。称取10.0克Al2O3(20~40目),配置8ml含4.93克Co(NO3)2.6H2O和0.58克(NH4)2HPO4的水溶液,滴加约2ml浓HNO3,加热溶解,用此水溶液浸渍上述Al2O3载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
实施例11
实施例11的催化剂为CoP/Al2O3(Co/P=4摩尔比)。称取10.0克Al2O3(20~40目),配置15ml含4.93克Co(NO3)2.6H2O的水溶液,加热溶解倒入上述Al2O3载体,搅拌下滴加氨水,沉淀沉积在Al2O3载体上,干燥,焙烧后,称取0.58克(NH4)2HPO4溶于8ml水中,加热溶解,用此水溶液浸渍上述载有CoO的Al2O3载体,60℃水浴烘干,120℃烘箱烘干8小时,450℃焙烧4h,由此制备出该催化剂的氧化态前驱物。
上述实施例1~11中的催化剂的氧化态前驱物每种使用前,在固定床反应器(直径为9mm:催化剂高度为5cm)中H2(GHSV=10000h-1)流中进行原位还原活化,条件为:常压,5℃/min从室温升温至350℃,1℃/min从350℃升温至650℃保持3小时在H2流中降温至反应温度,得到所述的催化剂。CO加氢反应条件为:固定床反应器(直径为9mm:催化剂高度为5cm)280℃,5.0Mpa,H2/CO(摩尔比为2∶1)混合气GHSV=5000h-1,反应尾气经冷阱去离子水充分吸收后,气相产物进行在线分析,色谱仪器为安捷伦3000A Micro GC,分子筛,Plot Q,Al2O3和OV-1四根毛细管柱,TCD检测器。水相产物离线分析,FFAP毛细管色谱柱,FID检测器。内标法分析,正戊醇为内标物。
反应结果总结在表1中。
实施例12
实施例5催化剂使用的氧化态前驱物前,在石英固定床反应器(直径为4cm:催化剂高度约为10cm)中H2(GHSV=10000h-1)流中进行原位还原活化,条件为:常压,5℃/min从室温升温至350℃,1℃/min从350℃升温至650℃保持3小时在H2流中降温至室温,在Ar流保护下转移至1立升容积的浆态床反应器中,在H2流中(GHSV=10000h-1)升温至反应温度。CO加氢反应条件为:浆态床反应器(直径为8.2cm:催化剂装量为70克,浆态液中催化剂含量为:10(重量)%,转速为900转/分),280℃,5.0Mpa,H2/CO(摩尔比为2∶1)混合气GHSV=5000h-1,反应尾气经冷阱去离子水充分吸收后,气相产物进行在线分析,色谱仪器为安捷伦3000A MicroGC,分子筛,Plot Q,Al2O3和OV-1四根毛细管柱,TCD检测器。水相产物离线分析,FFAP毛细管色谱柱,FID检测器。内标法分析,正戊醇为内标物。同时对浆态床反应器中的浆态液取样分析,分析结果合并后归一化处理得到反应结果。
反应结果总结在表1中。
表1:上述实施例催化剂的CO加氢反应结果
*基于CO摩尔数计算
**除了甲烷以外的烷烃
**除了甲醇、乙醇之外的含氧产物,碳数不超过5。
Claims (10)
1.一种负载型催化剂,所述负载型催化剂用于将合成气原料转化为烃类和含氧化物,其中:
所述负载型催化剂包括活性组分和载体;
所述活性组分为由过渡金属及所述过渡金属的磷化物组成的混合物,其中所述过渡金属是Fe、Co和Ni中的一种或多种,其中所述活性组分的重量百分比按金属计为催化剂重量的0.5~30.0%,其中在所述活性成分中,过渡金属原子的摩尔数与磷原子的摩尔数之比在1~10的范围内;并且
所述载体为SiO2或Al2O3;
其中SiO2的比表面积为100~600m2/g,并且平均孔径为5~90nm;并且Al2O3的比表面积为100~400m2/g,并且平均孔径为4~90nm。
2.根据权利要求1所述的催化剂,其中,所述活性组分重量百分比按金属计为催化剂重量的1.0~25.0%。
3.根据权利要求1所述的催化剂,其中,SiO2比表面积为200~400m2/g,并且平均孔径为10~50nm。
4.根据权利要求1所述的催化剂,其中,Al2O3的比表面积为150~300m2/g,并且平均孔径为10~50nm。
5.根据权利要求1所述的催化剂,其中,所述负载型催化剂由活性组分和载体两部分组成。
6.一种用于制备烃类和含氧化物的方法,所述方法包括:在反应器中,在权利要求1至5中任何一项所述的催化剂存在下,使合成气原料转化为烃类和含氧化物。
7.权利要求6所述的方法,其中,所述反应器为固定床或浆态床反应器。
8.权利要求6所述的方法,其中,所述方法在100~400℃的温度,1.0~10.0MPa表压的反应压力,合成气中的CO/H2按摩尔比计为0.5/1至10/1且空速为100~10000h-1的条件下进行。
9.一种用于制备权利要求1所述催化剂的方法,所述方法包括:将所述活性组分经由浸渍法或沉淀法中的一种或两种负载在所述载体上,然后高温空气中焙烧。
10.根据权利要求9所述的方法,所述方法还包括将焙烧后的催化剂在H2流中程序升温还原。
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