CN108816275A - 一种用于合成气制吡啶碱的催化剂及制备方法和应用 - Google Patents

一种用于合成气制吡啶碱的催化剂及制备方法和应用 Download PDF

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CN108816275A
CN108816275A CN201810353733.1A CN201810353733A CN108816275A CN 108816275 A CN108816275 A CN 108816275A CN 201810353733 A CN201810353733 A CN 201810353733A CN 108816275 A CN108816275 A CN 108816275A
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catalyst
auxiliary agent
molecular sieve
pyridine base
synthesis gas
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CN108816275B (zh
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刘小攀
罗超然
薛谊
王文魁
杜翔
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NANJING RED SUN BIOLOGICAL CHEMICAL CO Ltd
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Abstract

本发明公开了一种用于合成气制吡啶碱的催化剂，包括载体、活性组分、第一助剂与第二助剂；载体为分子筛，活性组分为Rh，第一助剂为Mn、Fe、Na、La中的一种或多种，第二助剂为Zn、Co、Cr、Bi、Cu中的一种或多种；Rh为载体质量的0.5～3％，第一助剂为载体质量的0.05～5％，第二助剂为载体质量的0.5～15％。本发明还公开了该催化剂在催化合成气制备吡啶碱中的应用，以合成气与供氨体为反应原料，反应得到吡啶碱产物。本发明催化剂可将一氧化碳加氢生成乙醛与醛氨的环化缩合反应耦合，经一步催化实现由合成气到吡啶碱的转化，一氧化碳的转化率在8～20％，吡啶碱的选择性为10～18％。

Description

一种用于合成气制吡啶碱的催化剂及制备方法和应用
技术领域
本发明属于催化剂技术领域，具体涉及一种用于合成气制吡啶碱的催化剂及制备方法和应用。
背景技术
吡啶碱俗称为杂环类三药与三药中间体的“芯片”，是国家重点鼓励的杂环类农药、医药及兽药等三药与三药中间体的含氮杂环类化合物，也是日用化工、食品与饲料添加剂的重要原料。
目前，ZSM-5分子筛催化醛与氨环化缩合生成吡啶类化合物是工业上生产吡啶碱最常用的方法。乙醛作为反应中的重要原料，在工业上通常采用乙烯氧化法、乙醇氧化法或乙炔合成法生产。这些工艺虽然发展较为成熟，但也有能耗高、对石油资源依赖较大等不足。合成气是一种以一氧化碳与氢气为主要组分的混合物，具有来源广泛、价格低廉等特点。探索以合成气制吡啶碱的新工艺对吡啶产业以及C1化工领域都有及其重要的意义。
迄今为止，尚未有用于合成气制吡啶碱的催化剂及相关工艺的报道，但有较多合成气制C2含氧化合物的报道。中国专利CN1354043A公布了一种用于合成气制备二碳含氧化合物的铑基催化剂，该催化剂采用硅铝比较高的MCM-41或MCM-22为载体，C2含氧化合物的选择性最高为55.4％。中国专利CN1175479A公开了一种一氧化碳加氢制乙醇、乙醛等二碳含氧化合物催化剂，所述催化剂为Rh-V-M/SiO2催化剂体系，M为Ru、Fe、Ir、Mo、Mn、K、Li、Zr或Cu元素中的一种或几种混合元素，该催化剂可使一氧化碳与氢气高效的转化为乙醇、乙醛产物，1％Rh-1.5％V-0.5％Fe-0.1％Ir-0.1％K/SiO2催化剂的乙醇与乙醛选择性为86％。
发明内容
本发明的目的是提供一种用于合成气制吡啶碱的催化剂，该催化剂可将一氧化碳、氢气、氨经一步催化生成吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶等吡啶碱产物。
本发明的目的是通过如下技术方案实现的：
一种用于合成气制吡啶碱的催化剂，所述的催化剂包括载体、活性组分、第一助剂与第二助剂；所述的载体为分子筛；所述的活性组分为Rh；所述的第一助剂为Mn、Fe、Na、La中的一种或多种，优选为Mn与选自Fe、Na、La中的至少一种；所述的第二助剂为Zn、Co、Cr、Bi、Cu中的一种或多种。
所述的活性组分Rh的含量为载体质量的0.5～3％，优选为1～3％；所述的第一助剂为载体质量的0.05～5％，优选为1.5～5％；所述的第二助剂为载体质量的0.5～15％，优选为5～11％。
所述的分子筛为HZSM-5分子筛、HZSM-11分子筛、HZSM-35分子筛与MCM-22分子筛中的一种或多种；优选为硅铝比为50～150的HZSM-5分子筛、HZSM-11分子筛、HZSM-35分子筛与MCM-22分子筛中的一种或多种；进一步优选为硅铝比为50～150的HZSM-5分子筛、HZSM-11分子筛中的一种或多种。
本发明的另一个目的是提供用于合成气制吡啶碱的催化剂的制备方法，包括：
步骤(1)、将铑盐、第一助剂和第二助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将载体与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、将步骤(1)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂；
或步骤(1)、将铑盐溶解于溶剂中获得铑盐溶液，将载体与铑盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、步骤(1)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，制得负载有活性组分铑的前驱体；
步骤(3)、将助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将步骤(2)制得的前驱体与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(4)、步骤(3)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂；
或步骤(1)、将助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将分子筛与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、步骤(1)中获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1-5h，制得负载有助剂的前驱体；
步骤(3)、将铑盐溶解于溶剂中搅拌获得铑盐溶液，将步骤(2)制得的前驱体与铑盐溶液混合均匀，室温浸渍0.5～48h；
步骤(4)、步骤(3)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂。
所述的铑盐为氯化铑，第一助剂Mn、Fe、Na、La对应的金属盐为硝酸盐；第二助剂Zn、Co、Cr、Bi、Cu对应的金属盐为硝酸盐。
所述的溶剂为去离子水、甲醇、乙醇、异丙醇中的一种或多种。
本发明所述的催化剂在催化合成气制备吡啶碱中的应用。
一种采用本发明所述的催化剂催化合成气制备吡啶碱的方法，包括：以合成气与供氨体为反应原料，所述的合成气中H2与CO的摩尔比为1～5:1，所述的供氨体以NH3计与CO的摩尔比为1:1～100，反应原料以空速5000～15000h-1通入装填有本发明所述的催化剂的固定床反应器，在反应温度为250～400℃，反应压力为1～5MPa下反应得到吡啶碱产物，吡啶碱产物经去离子水吸收。
所述的供氨体选自氨气、液氨、氨水中的一种或多种。
所述的吡啶碱为吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶中的一种或多种。
本发明所述的催化剂中活性组分、第一助剂与第二助剂以金属单质或氧化物形式存在。所述的催化剂在使用前采用氢气进行还原处理，还原处理的方式为：催化剂装填于固定床反应器的恒温段，氢气空速500～1200h-1，还原温度250～450℃，还原时间1～5h。
本发明的有益效果为：
本发明催化剂中Rh与第一助剂共同催化一氧化碳与氢气高效的转化为乙醛与乙醇，在第二助剂参与下将生成的乙醇选择性氧化为乙醛，随后乙醛与氨在分子筛的酸性位点催化下生成吡啶碱产物。本发明催化剂可将一氧化碳加氢生成乙醛与醛氨的环化缩合反应耦合，经一步催化实现由合成气到吡啶碱的转化，一氧化碳的转化率在8～20％之间，吡啶碱的选择性为10～18％，吡啶碱的选择性显著高于只含有第一助剂或第二助剂的催化剂。
同时，本发明为吡啶碱的生产以及合成气的深层次利用提供了新思路，具有广阔的市场前景。
具体实施方式
下面结合实施例对本发明的技术方案进行具体描述。
实施例1
步骤(1)、将0.1283g RhCl3·3H2O，0.3914g Mn(NO3)2·6H2O，0.0361g Fe(NO3)3·9H2O，0.0311g La(NO3)3·6H2O，1.1423g Zn(NO3)2·6H2O溶解于5g无水乙醇中搅拌均匀，获得均一的金属盐溶液，将5g HZSM-5分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍4h；
步骤(2)、将步骤(1)获得的混合物在80℃下真空干燥2h，350℃下焙烧2h，记作1.0Rh-1.5Mn-0.1Fe-0.2La-5.0Zn/HZSM-5(1.0Rh表示Rh原子质量占载体质量的1％，下同)。
实施例2
步骤(1)、将0.1919g RhCl3·3H2O，0.3914g Mn(NO3)2·6H2O，0.1083g Fe(NO3)3·9H2O，0.4932g Co(NO3)2·6H2O，3.8462g Cr(NO3)3·9H2O溶解于5g乙醇中搅拌均匀，获得均一的金属盐溶液，将5g HZSM-11分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在100℃下真空干燥1h，400℃下焙烧1.5h，记作1.5Rh-1.5Mn-0.3Fe-2.0Co-10Cr/HZSM-11。
实施例3
步骤(1)、将0.1577g Rh(NO3)3·2H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将5g HZSM-35分子筛(硅铝比120)与氯化铑溶液混合均匀；
步骤(2)、将步骤(1)获得的混合物室温浸渍2h，100℃下真空干燥0.5h，500℃下焙烧4h制得前驱体1.0Rh/HZSM-35；
步骤(3)、将0.1305g Mn(NO3)2·6H2O，0.9018g Fe(NO3)3·9H2O，0.1142g Zn(NO3)2·6H2O，1.9231g Cr(NO3)3·9H2O，0.3766g Cu(NO3)2·3H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将步骤(2)制得的前驱体1.0Rh/HZSM-35与金属盐溶液混合均匀后室温浸渍2h；
步骤(4)、将步骤(3)获得的混合物在100℃下真空干燥0.5h，500℃下焙烧4h，记作1.0Rh-0.05Mn-2.5Fe-0.5Zn-2.0Cu-5.0Cr/HZSM-35。
实施例4
步骤(1)、将0.1921g RhCl3·3H2O溶解于5g乙醇中搅拌均匀，获得均一的氯化铑溶液，将5g HZSM-5分子筛(硅铝比120)与氯化铑溶液混合均匀；
步骤(2)、将步骤(2)获得的混合物室温浸渍24h，110℃下真空干燥3h，550℃下焙烧3h制得前驱体1.5Rh/HZSM-5；
步骤(3)、将0.6523gMn(NO3)2·6H2O，0.3115gLa(NO3)3·6H2O，2.4661g Co(NO3)2·6H2O溶解于5g乙醇中搅拌均匀，获得均一的金属盐溶液，将步骤(2)制得的前驱体1.5Rh/HZSM-5与金属盐溶液混合均匀后室温浸渍24h；
步骤(4)、将步骤(3)获得的混合物在110℃下真空干燥3h，550℃下焙烧3h，记作1.5Rh-2.5Mn-2.0La-10.0Co/HZSM-5。
实施例5
步骤(1)、将0.1577g Rh(NO3)3·2H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将5g HZSM-11分子筛(硅铝比120)与氯化铑溶液混合均匀后室温浸渍48h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，300℃下焙烧3h制得前驱体1.0Rh/HZSM-11；
步骤(3)、将0.3914g Mn(NO3)2·6H2O，0.0361g Fe(NO3)3·9H2O，0.0580g Bi(NO3)3·5H2O，1.9009g Cu(NO3)2·3H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将步骤(2)制得的1.0Rh/HZSM-11前驱体与金属盐溶液混合均匀后室温浸渍48h；
步骤(4)、将步骤(3)获得的混合物在120℃下真空干燥3h，300℃下焙烧3h，记作1.0Rh-1.5Mn-0.1Fe-0.5Bi-10.0Cu/HZSM-11。
实施例6
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.0184g NaNO3，2.2846g Zn(NO3)2·6H2O，0.0941g Cu(NO3)2·3H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5gHZSM-11分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍8h；
步骤(2)、将步骤(1)获得的混合物在100℃下真空干燥4h，350℃下焙烧2.5h制得前驱体1.5Mn-0.1Na-10.0Zn-0.5Cu/HZSM-11；
步骤(3)、将0.3837g RhCl3·3H2O，溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.1Na-10.0Zn-0.5Cu/HZSM-11与氯化铑溶液混合均匀后室温浸渍8h；
步骤(4)、将步骤(3)获得的混合物在100℃下真空干燥4h，350℃下焙烧2.5h，记作3.0Rh-1.5Mn-0.1Na-10.0Zn-0.5Cu/HZSM-11。
实施例7
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.1233g Co(NO3)2·6H2O，0.1923g Cr(NO3)3·9H2O，0.5801g Bi(NO3)3·5H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5g MCM-22分子筛(硅铝比50)与金属盐溶液混合均匀后室温浸渍15h；
步骤(2)、将步骤(1)获得的混合物在100℃下真空干燥4h，400℃下焙烧2h制得前驱体1.5Mn-0.5Co-5.0Bi-0.5Cr/MCM-22；
步骤(3)、将0.0642g RhCl3·3H2O，溶解于5g乙醇中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.5Co-5.0Bi-0.5Cr/MCM-22与氯化铑溶液混合均匀后室温浸渍15h；
步骤(4)、将步骤(3)获得的混合物在100℃下真空干燥4h，400℃下焙烧2h，记作0.5Rh-1.5Mn-0.5Co-5.0Bi-0.5Cr/MCM-22。
实施例8
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.0722g Fe(NO3)3·9H2O，0.0184g NaNO3，1.1602g Bi(NO3)3·5H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5gHZSM-5分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h制得前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/HZSM-5；
步骤(3)、将0.2547g RhCl3·3H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/HZSM-5与氯化铑溶液混合均匀后室温浸渍10h；
步骤(4)、将步骤(3)中获得的混合物在120℃下真空干燥3h，450℃下焙烧5h，记作2.0Rh-1.5Mn-0.2Fe-0.1Na-10.0Bi/HZSM-5。
对比例1
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.0722g Fe(NO3)3·9H2O，0.0184g NaNO3溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5g HZSM-5分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h制得前驱体1.5Mn-0.2Fe-0.1Na/HZSM-5；
步骤(3)、将0.2547g RhCl3·3H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.2Fe-0.1Na/HZSM-5与氯化铑溶液混合均匀后室温浸渍10h；
步骤(4)、将步骤(3)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h，记作2.0Rh-1.5Mn-0.2Fe-0.1Na/HZSM-5。
对比例2
步骤(1)、1.1602g Bi(NO3)3·5H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5g HZSM-5分子筛(硅铝比120)与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h制得前驱体10.0Bi/HZSM-5；
步骤(3)、将0.2547g RhCl3·3H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体10.0Bi/HZSM-5与氯化铑溶液混合均匀后室温浸渍10h；
步骤(4)、将步骤(3)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h，记作2.0Rh-10.0Bi/HZSM-5。
对比例3
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.0722g Fe(NO3)3·9H2O，0.0184g NaNO3，1.1602g Bi(NO3)3·5H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5gMCM-41分子筛(全硅分子筛)与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h制得前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/MCM-41；
步骤(3)、将0.2547g RhCl3·3H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/MCM-41与氯化铑溶液混合均匀后室温浸渍10h；
步骤(4)、将步骤(3)中获得的混合物在120℃下真空干燥3h，450℃下焙烧5h，记作2.0Rh-1.5Mn-0.2Fe-0.1Na-10.0Bi/MCM-41。
对比例4
步骤(1)、将0.3914g Mn(NO3)2·6H2O，0.0722g Fe(NO3)3·9H2O，0.0184g NaNO3，1.1602g Bi(NO3)3·5H2O溶解于5g去离子水中搅拌均匀，获得均一的金属盐溶液，将5gSiO2与金属盐溶液混合均匀后室温浸渍10h；
步骤(2)、将步骤(1)获得的混合物在120℃下真空干燥3h，450℃下焙烧5h制得前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/SiO2；
步骤(3)、将0.2547g RhCl3·3H2O溶解于5g去离子水中搅拌均匀，获得均一的氯化铑溶液，将步骤(2)制得的前驱体1.5Mn-0.2Fe-0.1Na-10.0Bi/SiO2与氯化铑溶液混合均匀后室温浸渍10h；
步骤(4)、将步骤(3)中获得的混合物在120℃下真空干燥3h，450℃下焙烧5h，记作2.0Rh-1.5Mn-0.2Fe-0.1Na-10.0Bi/SiO2。
催化剂性能考察
使用固定床反应器评价实施例1-8与对比例1-4制备得到的催化剂的催化性能。
具体方法为：取1.5g压片破碎至20-40目的催化剂装填于固定床反应器的恒温段，反应器采用内径为19mm、管长为700mm的反应管。反应开始前采用纯氢气对催化剂进行还原，氢气空速800h-1，还原温度350℃，还原时间3h。还原结束后降温至320℃，通入H2/CO＝2:1的合成气，使***压力升至3.0MPa后，按照CO:NH3＝10:1(摩尔比)通入液氨，反应原料总空速为8000h-1；含有吡啶碱的混合产物经去离子水吸收，反应3h后分别对水相中的吡啶碱产物与不凝气中的一氧化碳进行分析并对比其反应结果。
合成气制吡啶碱反应是Rh活性位催化一氧化碳加氢与酸性位催化醛氨缩合的串联反应，Rh活性位与载体的酸性位为缺一不可。由表1可知，选取HZSM-5分子筛、HZSM-11分子筛、HZSM-35分子筛为催化剂载体，由于载体具有适宜的孔结构与酸性位点，Rh在第一助剂与第二助剂的协同作用下催化一氧化碳与氢气生成乙醛，再进一步发生醛氨缩合反应生成吡啶碱产物。MCM-22分子筛虽然具有合适酸强度，但由于具有较大的十二元环超笼结构，乙醛与氨易在超笼中发生深度脱氢等副反应生成大分子积碳堵塞孔道，CO的转化率相对HZSM分子筛较低，但仍能够获得较为理想的催化效果。而以MCM-41与SiO2为载体，由于其酸性较弱，难以催化乙醛与氨进一步发生醛氨缩合反应。
表1催化剂性能考察

Claims (10)

1.一种用于合成气制吡啶碱的催化剂，其特征在于所述的催化剂包括载体、活性组分、第一助剂与第二助剂；所述的载体为分子筛；所述的活性组分为Rh；所述的第一助剂为Mn、Fe、Na、La中的一种或多种；所述的第二助剂为Zn、Co、Cr、Bi、Cu中的一种或多种。
2.根据权利要求1所述的催化剂，其特征在于所述的活性组分Rh为载体质量的0.5～3％；所述的第一助剂为载体质量的0.05～5％；所述的第二助剂为载体质量的0.5～15％。
3.根据权利要求2所述的催化剂，其特征在于根据权利要求1所述的催化剂，其特征在于所述的活性组分Rh为载体质量的1～3％；所述的第一助剂为载体质量的1.5～5％；所述的第二助剂为载体质量的5～11％。
4.根据权利要求1所述的催化剂，其特征在于所述的分子筛为HZSM-5分子筛、HZSM-11分子筛、HZSM-35分子筛与MCM-22分子筛中的一种或多种；优选为硅铝比为50～150的HZSM-5分子筛、HZSM-11分子筛、HZSM-35分子筛与MCM-22分子筛中的一种或多种；进一步优选为硅铝比为50～150的HZSM-5分子筛、HZSM-11分子筛中的一种或多种。
5.权利要求1所述的用于合成气制吡啶碱的催化剂的制备方法，其特征在于包括：
步骤(1)、将铑盐、第一助剂和第二助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将载体与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、将步骤(1)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂；
或步骤(1)、将铑盐溶解于溶剂中获得铑盐溶液，将载体与铑盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、步骤(1)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，制得负载有活性组分铑的前驱体；
步骤(3)、将助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将步骤(2)制得的前驱体与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(4)、步骤(3)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂；
或步骤(1)、将助剂对应的金属盐溶解于溶剂中获得金属盐溶液，将分子筛与金属盐溶液混合均匀，室温浸渍0.5～48h；
步骤(2)、步骤(1)中获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1-5h，制得负载有助剂的前驱体；
步骤(3)、将铑盐溶解于溶剂中搅拌获得铑盐溶液，将步骤(2)制得的前驱体与铑盐溶液混合均匀，室温浸渍0.5～48h；
步骤(4)、步骤(3)获得的混合物在80～120℃下真空干燥0.5～4h，300～550℃下焙烧1～5h，获得用于合成气制吡啶碱的催化剂。
6.根据权利要求5所述的催化剂的制备方法，其特征在于所述的铑盐为氯化铑；第一助剂Mn、Fe、Na、La对应的金属盐为硝酸盐；第二助剂Zn、Co、Cr、Bi、Cu对应的金属盐为硝酸盐；所述的溶剂为去离子水、甲醇、乙醇、异丙醇中的一种或多种。
7.权利要求1所述的催化剂在催化合成气制备吡啶碱中的应用。
8.一种采用权利要求1所述的催化剂催化合成气制备吡啶碱的方法，其特征在于包括：以合成气与供氨体为反应原料，所述的合成气中H2与CO的摩尔比为1～5:1，所述的供氨体以NH3计与CO的摩尔比为1:1～100；反应原料以空速5000～15000h-1，通入装填有权利要求1所述的催化剂的固定床反应器，在反应温度为250～400℃、反应压力为1～5MPa下反应得到吡啶碱产物。
9.根据权利要求8所述的合成气制备吡啶碱的方法，其特征在于所述的供氨体选自氨气、液氨、氨水中的一种或多种；所述的吡啶碱产物包含吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶中的一种或多种。
10.根据权利要求8所述的合成气制备吡啶碱的方法，其特征在于所述的催化剂在使用前采用氢气进行还原处理，还原处理的方式为：催化剂装填于固定床反应器的恒温段，氢气空速500～1200h-1，还原温度250～450℃，还原时间1～5h。
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