CN106391016B - 费托合成单分散铁基催化剂及其制备方法和应用 - Google Patents

费托合成单分散铁基催化剂及其制备方法和应用 Download PDF

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CN106391016B
CN106391016B CN201610785839.XA CN201610785839A CN106391016B CN 106391016 B CN106391016 B CN 106391016B CN 201610785839 A CN201610785839 A CN 201610785839A CN 106391016 B CN106391016 B CN 106391016B
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ferrum
based catalyst
synthesis
iron
monodisperse
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CN106391016A (zh
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郭立
陈建刚
张岩丰
金家琪
石友良
郑申棵
龚焱
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Abstract

本发明公开了一种费托合成单分散铁基催化剂及其制备方法和应用，该催化剂包括载体二氧化硅和活性组分铁，载体二氧化硅呈介孔球状颗粒结构，载体二氧化硅包裹活性组分铁，活性组分铁呈纳米颗粒状且分布均匀；载体二氧化硅颗粒粒径为140～160nm。制备方法中通过调节CO2的压力使催化剂的形貌从碟片状堆积变为均一的球状，从而将铁纳米颗粒包裹在球状二氧化硅内部，阻止了铁纳米颗粒的烧结，也避免了难还原成份的出现；将本发明的铁基催化剂应用于α‑烯烃的制备，从而提供了一种生产α‑烯烃的新工艺路线，它以合成气为原料，在本发明的铁基催化剂的作用下，直接合成α‑烯烃。该铁基催化剂性能优良，长链α‑烯烃选择性高。

Description

费托合成单分散铁基催化剂及其制备方法和应用
技术领域
本发明涉及费托合成领域，具体地指一种费托合成单分散铁基催化剂及其制备方法和应用。
背景技术
长链α-烯烃是指不饱和键位于链烃端位的碳四以上、碳十六以下的单烯烃或混合烯烃。由于分子中具有活性位(烯键)，α-烯烃容易接入各种官能团，衍化成醇、酸及酯等化合物，广泛应用于表面活性剂、增塑剂等精细化学品生产。
目前α-烯烃主要作为共聚单体用于生产聚乙烯，占总消费量的44.1％，用于共聚单体的最为广泛的品种是C4(1-丁烯)、C6(1-己烯)和C8(1-辛烯)，在生产高密度聚乙烯和线性低密度聚乙烯(HDPE/LLDPE)中使用这些共聚单体可改善PE密度，提高其抗撕裂和拉伸强度。其次，α-烯烃也用于生产高碳醇，最终产品为增塑剂和洗涤剂，占总消费量的19.6％，高碳醇是表面活性剂和增塑剂的基础原料，世界每年消耗量已达千万吨左右，其中，辛醇主要用于制备各种酯类，每年在全世界销售额约十多亿美元；庚醇可用于制备香料和香精，价值很高。再有，α-烯烃还用于生产聚α-烯烃(PAO)，占总消费量的16.6％，PAO是高端润滑油基础油的原料，其黏度指数高，价格是矿物油的2-3倍。此外，α-烯烃也作为乳化剂、皮革处理剂、润滑油添加剂、防锈剂、织物整理剂及纸张等化工原料。目前，国外α-烯烃总生产能力约为212万吨，国内生产能力约为26万吨。并且，国内缺乏生产长链α-烯烃的能力，1-辛烯和1-己烯几乎完全依赖进口。
传统的α-烯烃生产工艺有石蜡裂解法或乙烯齐聚法。其中，石蜡裂解法一般采用于脱油精制蜡为原料，原料蜡预热后与蒸汽混合，于550℃下在管式裂解炉中进行反应；乙烯齐聚法生产α-烯烃，乙烯齐聚反应时在三乙基铝催化剂作用下，乙烯发生受控链增长反应，聚合成一定链长的烯烃，具体又可分成两步法、一步法及SHOP工艺等。这种传统的α-烯烃生产工艺基于蜡或乙烯，原料来源石油，伴随着世界范围内油气资源的萎缩，这种生产工艺急需转型。因此，国内外正在进行着能源原材料的多样化改革，煤、生物质或天然气通过合成气间接转化为清洁液体燃料和化学品的非石油路线日益受到重视。
另外，在近年有关α-烯烃的研究中，按核心技术路线的差异分类，烯烃制备技术大致分为以下几种类型类型。第一种，以中国专利申请CN101265151A为代表公开的从甲醇或二甲醚制备轻烯烃的方法，将甲醇或二甲醚原料通过进料分布器送入反应器的反应区中，与分子筛催化剂接触，生成包括含轻烯烃、二烯烃、含氧化合物、碳四烃的混合物。第二种，以中国专利申请CN101265149A和CN1537674A为代表公开的从合成气直接制取乙烯、丙烯、丁烯反应的铁/活性炭催化剂，其特征在于自制催化剂的特定化学组成。第三种，以中国专利申请CN1444551A，CN1545520A，CN1443149A及CN1440311A为代表公开的从乙烯低聚生产直链α-烯烃用于配位体及催化剂体系和工艺。第四种，以中国专利申请CN1403425A和CN1421424A为代表公开的蜡裂解制α-烯烃或从高碳烷基铝制备高碳α-烯烃的方法及设备。第五种，以中国专利申请CN1284898A和CN1515359A为代表公开的一种生产用于费托浆态床工艺的自支撑型沉淀铁剂催化剂颗粒的方法。
这些α-烯烃制备技术中，除了与传统方法一样依托于日渐萎缩的石油原料的一类制备方法外，还有一类是通过费托合成来实现的，费托合成是将煤，天然气，石油焦及其他含碳原料制得的合成气(CO/H2)转化成高质量清洁能源的一项技术，费托反应是一个复杂的过程，产物包含烷烃，烯烃，醛，醇及有机酸等多种有机化物。依靠费托合成制备α-烯烃的过程中经常会用到铁基催化剂，但是，现有的铁基催化剂在反应过程中铁纳米颗粒容易聚集长大而导致催化剂活性降低，催化剂的稳定性和长链α-烯烃的选择性均不高。
发明内容
本发明的目的就是要提供一种费托合成单分散铁基催化剂及其制备方法和应用，该铁基催化剂性能优良，长链α-烯烃选择性高。
为实现上述目的，本发明采用的技术方案是：一种费托合成单分散铁基催化剂，包括载体二氧化硅和活性组分铁，其特征在于：所述载体二氧化硅呈介孔球状颗粒结构，所述载体二氧化硅包裹所述活性组分铁，所述活性组分铁呈纳米颗粒状且分布均匀；所述载体二氧化硅颗粒粒径为140～160nm，所述载体二氧化硅的介孔孔径为2～9nm。
进一步地，所述活性组分铁占催化剂总重量的5～40％，其余为载体二氧化硅。
进一步地，所述载体二氧化硅颗粒粒径为150～160nm，所述载体二氧化硅的介孔孔径为2.1～5.7nm。
更进一步地，所述载体二氧化硅颗粒粒径为150～155nm，所述载体二氧化硅的介孔孔径为3.3～4.1nm。
一种上述费托合成单分散铁基催化剂的制备方法，包括以下步骤：
1)将乙醇与水按1～10：1～10的体积比混合制得乙醇水溶液，然后往所述乙醇水溶液中加入0.005～0.02g/ml的有机胺混合均匀，制得混合溶液；
2)往步骤1)所得混合溶液中加入铁纳米粒并滴加0.05～0.2g/ml的正硅酸四乙酯；
3)往步骤2)所得产物中通入1～15MPa的CO2并升温至35～45℃进行化学反应，待反应结束后，冷却并放出CO2；
4)将步骤3)所得固体产物水洗干燥后进行高温焙烧，即可得到所述费托合成单分散铁基催化剂。
进一步地，所述步骤3)在高压反应釜中进行，通入6～9MPa的CO2并升温至40～45℃，搅拌反应22～26h。
进一步地，所述步骤4)中，焙烧温度为500～560℃，焙烧时间为4.5～5.5h。
进一步地，所述步骤2)中，铁纳米粒按铁的负载量为5～40wt％加入。
一种上述费托合成单分散铁基催化剂的应用，将所述费托合成单分散铁基催化剂用于以合成气为原料费托合成α-烯烃，费托合成反应条件为：反应温度为190～360℃，反应压力为0.5～5.0MPa，进气体积空速为400～20000h-1，搅拌转速为400～1400rpm，H2与CO进料体积比为1∶1～3∶1。
进一步，所述费托合成单分散铁基催化剂的还原条件为：还原温度为300～500℃，还原压力为0.2～1.2MPa，搅拌转速为400～1400rpm，进气体积空速为400～3500h-1，反应时间为6～18h，纯氢气或合成气氛。
与现有技术相比，本发明具有以下优点：
其一，本发明的铁基催化剂由于载体具有较大孔径的介孔和铁纳米颗粒大小均一，使得催化剂的还原程度和炭化程度易于调控；均一球状的二氧化硅载体将铁纳米颗粒包裹在球状二氧化硅内部，阻止了铁纳米颗粒的烧结，也避免了难还原成份的出现，使得本发明的铁基催化剂性能优良，长链α-烯烃选择性高；在介孔球状二氧化硅里面包裹铁纳米颗粒且分布均匀，这种结构使得铁催化活性中心更为一致，有利于活性中心的构建。同时，较大的介孔利于底物和产物分子的扩散，孔道的大小对产物的选择性起到调节作用，从而进一步提高了铁基催化剂的α-烯烃选择性。
其二，本发明铁基催化剂制备过程中使用压缩的CO2诱导形成水包二氧化碳的微乳液体系为模板合成核壳结构的催化剂，与传统方法相比，本发明所得催化剂的形貌通过CO2的压力来调控，同时引入CO2还能起到扩孔作用，省去了传统制备方法中的酸、碱及有机扩孔剂；本发明通过调节CO2的压力使催化剂的形貌从碟片状堆积变为均一的球状，从而将铁纳米颗粒包裹在球状二氧化硅内部，阻止了铁纳米颗粒的烧结，也避免了难还原成份的出现，从而提升了催化剂的活性与α-烯烃选择性。
其三，本发明制得的铁基催化剂可以通过粉末压片成型，也可通过喷雾干燥成型，具有良好的机械性能。
其四，本发明催化剂的单分散结构特征和适宜的金属-载体化学作用，使得铁基催化剂产生适合α-烯烃生成的活性中心，因而具有高的α-烯烃选择性；本发明提供了一种生产α-烯烃的新工艺路线，它以合成气为原料，在本发明的铁基催化剂的作用下，直接合成α-烯烃。
其五，本发明变废为宝，将CO2应用于催化新材料的制备，利用二氧化碳作为调控开关，减少无机矿物酸的使用，进行催化剂的绿色合成，赋予了CO2新的用途。
附图说明
图1为实施例1中未充入CO2或CO2压力很小时铁基催化剂结构的SEM照片。
图2为实施例1中费托合成单分散铁基催化剂结构的SEM照片。
图3为实施例1中费托合成单分散铁基催化剂结构的TEM照片。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明，便于更清楚地了解本发明，但它们不对本发明构成限定。
实施例1
称取1.22克十二胺加入到10ml乙醇和90ml水中室温搅拌1h；然后加入0.59g铁纳米颗粒和8.16g正硅酸四乙酯；接着将得到的混合物转移到高压反应釜中，通入CO2并升温至40℃搅拌24h，此时CO2压力为1.0MPa，反应结束后，冷却并放出CO2；将得到的固体水洗抽滤数次，过夜干燥，将干燥得到的粉末在马弗炉中500℃焙烧5h；最后压片，筛分制得含Fe含量为20wt％的费托合成单分散铁基催化剂(20wt％Fe@SiO2-CO2-1)，随着CO2的增加催化剂从碟片状(如图1所示)的堆积转变成为均一球状颗粒的本发明铁基催化剂(如图2所示)，该铁基催化剂在介孔球状二氧化硅里面包裹铁纳米铁颗粒且分布均匀，载体二氧化硅颗粒粒径为150nm，载体二氧化硅的介孔孔径为2.5±0.4nm(如图3所示)。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述铁基催化剂，在纯氢气中程序升温还原，还原条件为：还原温度为400℃，压力为0.4MPa，空速为800h-1(V/V)，时间为12h；还原后，降温切换合成气进行反应，反应条件为：反应温度为260℃，压力为1.0MPa，空速为400h-1(V/V)，H2/CO＝3/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为：还原温度为400℃，压力为0.4MPa，空速为600h-1(V/V)，转速为600rpm，时间为12h；还原后，降温切换成合成气进行反应，反应条件为：温度为260℃，压力为1.0MPa，空速为700h-1(V/V)，转速为600rpm，H2/CO＝3/1。反应结果见表2。
实施例2
称取0.5克甲酰胺加入到90ml乙醇和10ml水中室温搅拌1h；然后加入0.34g铁纳米颗粒和5g正硅酸四乙酯；接着将得到的混合物转移到高压反应釜中，通入CO2并升温至45℃搅拌22h此时CO2压力为4.0MPa，反应结束后，冷却并放出CO2；将得到的固体水洗抽滤数次，过夜干燥，将干燥得到的粉末在马弗炉中560℃焙烧4.5h；压片，筛分制得Fe含量为20wt％的费托合成单分散铁基催化剂(20wt％Fe@SiO2-CO2-4)，载体二氧化硅颗粒粒径为155nm，载体二氧化硅的介孔孔径为3.7±0.4nm。
在加压固定床反应器中(Φ10×500mm)装填1.5ml60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为：温度为300℃，压力为1.2MPa，空速为3000h-1(V/V)，时间为12h；还原后，降温切换合成气进行反应，反应条件为：温度为260℃，压力为5.0MPa，空速为400h-1(V/V)，H2/CO＝2/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为：温度为300℃，压力为1MPa，空速为600h-1(V/V)，转速为600rpm，时间为12h；还原后，降温切换成合成气进行反应，反应条件为：温度为260℃，压力为1.0MPa，空速为700h-1(V/V)，转速为600rpm，H2/CO＝2/1。反应结果见表2。
实施例3
称取2克哌嗪加入到10ml乙醇和90ml水中室温搅拌1h；然后加入1.45g铁纳米颗粒和20g正硅酸四乙酯；接着将得到的混合物转移到高压反应釜中，通入CO2并升温至35℃搅拌26h，此时CO2压力为6.0MPa，反应结束后，冷却并放出CO2；将得到的固体水洗抽滤数次，过夜干燥，并将干燥得到的粉末在马弗炉中540℃焙烧5.5h；最后压片，筛分制得铁含量为20wt％的费托合成单分散铁基催化剂(20wt％Fe@SiO2-CO2-6)，载体二氧化硅颗粒粒径为160nm，所述载体二氧化硅的介孔孔径为4.6±0.4nm。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为：温度为500℃，压力为0.2MPa，空速为800h-1(V/V)，时间为12h；还原后，降温切换合成气进行反应，反应条件为：温度为230℃，压力为1.0MPa，空速为2000h-1(V/V)，H2/CO＝1/1。反应结果见表2。
取140目以上的上述铁基催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为：温度为400℃，压力为0.4MPa，空速为600h-1(V/V)，转速为600rpm，时间为12h；还原后，降温切换成合成气进行反应，反应条件为：温度为240℃，压力为1.0MPa，空速为3000h-1(V/V)，转速为600rpm，H2/CO＝1/1。反应结果见表2。
实施例4
称取1.5g苯胺加入到10ml乙醇和90ml水中室温搅拌1h；然后加入0.69g铁纳米颗粒和10g正硅酸四乙酯；接着将得到的混合物转移到高压反应釜中，通入CO2并升温至40℃搅拌24h，此时CO2压力为9.0MPa，反应结束后，冷却并放出CO2；将得到的固体水洗抽滤数次，过夜干燥，并将干燥得到的粉末在马弗炉中500℃焙烧5h；最后压片，筛分制得铁含量为20wt％的费托合成单分散铁基催化剂(Fe@SiO2-CO2-9)，载体二氧化硅颗粒粒径为155nm，载体二氧化硅的介孔孔径为5.3±0.4nm。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述铁基催化剂，在纯氢气中程序升温还原，还原条件为：温度为400℃，压力为0.4MPa，空速为800h-1(V/V)，时间为12h；还原后，降温切换合成气进行反应，反应条件为：温度为240℃，压力为1.0MPa，空速为800h-1(V/V)，H2/CO＝3/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为：温度为400℃，压力为0.4MPa，空速为600h-1(V/V)，转速为600rpm，时间为12h；还原后，降温切换成合成气进行反应，反应条件为：温度为260℃，压力为1.0MPa，空速为7000h-1(V/V)，转速为600rpm，H2/CO＝3/1。反应结果见表2。
实施例5
称取0.61克十二胺加入到10ml乙醇和90ml水中室温搅拌1h；然后加入0.59g铁纳米颗粒和8.16g正硅酸四乙酯；接着将得到的混合物转移到高压反应釜中，通入CO2并升温至40℃搅拌24h，此时CO2压力为4.0MPa，反应结束后，冷却并放出CO2；将得到的固体水洗抽滤数次，过夜干燥，并将干燥得到的粉末在马弗炉中500℃焙烧5h；最后压片，筛分制得铁含量为20wt％的费托合成单分散铁基催化剂(20wt％Fe@SiO2-CO2-4)，载体二氧化硅颗粒粒径为145nm，载体二氧化硅的介孔孔径为3.7±0.4nm。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述铁基催化剂，在纯氢气中程序升温还原，还原条件为：温度为400℃，0.4MPa，空速为800h-1(V/V)，时间为12h；还原后，降温切换合成气进行反应，反应条件为：温度为260℃，压力为1.0MPa，空速为12000h-1(V/V)，H2/CO＝3/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为：温度为400℃，压力为0.4MPa，空速为600h-1(V/V)，转速为600rpm，时间为12h；还原后，降温切换成合成气进行反应，反应条件为：温度为230℃，压力为1.0MPa，空速为1000h-1(V/V)，转速为600rpm，H2/CO＝3/1。反应结果见表2。
实施例6～10
实施例6～10与实施例5除铁基催化剂中的Fe含量及制备过程中CO2压力，反应温度，进气体积空速不同外其余均相同。Fe含量和制备过程中CO2压力见下表1；反应温度，进气体积空速及反应结果见下表2。
实施例1～10制得的铁基催化剂中的Fe含量及制备过程中CO2的压力如下表1所示。除所列组分外，其余组分为二氧化硅。
表1
实施例 Fe含量(wt％) CO<sub>2</sub>压力(MPa)
实施例1 20％ 1
实施例2 20％ 4
实施例3 20％ 6
实施例4 20％ 9
实施例5 20％ 4
实施例6 10％ 4
实施例7 10％ 1
实施例8 30％ 4
实施例9 30％ 1
实施例10 40％ 4
实施例1～10制得的铁基催化剂的烯烃合成反应性能见下表2。
表2

Claims (9)

1.一种费托合成单分散铁基催化剂，包括载体二氧化硅和活性组分铁，其特征在于：所述载体二氧化硅呈介孔球状颗粒结构，所述载体二氧化硅包裹所述活性组分铁，所述活性组分铁呈纳米颗粒状且分布均匀；所述载体二氧化硅颗粒粒径为140～160nm，所述载体二氧化硅的介孔孔径为2～9nm。
2.根据权利要求1所述的费托合成单分散铁基催化剂，其特征在于：所述活性组分铁占催化剂总重量的5～40％，其余为载体二氧化硅。
3.根据权利要求1或2所述的费托合成单分散铁基催化剂，其特征在于：所述载体二氧化硅颗粒粒径为150～160nm，所述载体二氧化硅的介孔孔径为2.1～5.7nm。
4.根据权利要求1或2所述的费托合成单分散铁基催化剂，其特征在于：所述载体二氧化硅颗粒粒径为150～155nm，所述载体二氧化硅的介孔孔径为3.3～4.1nm。
5.一种权利要求1所述费托合成单分散铁基催化剂的制备方法，包括以下步骤：
1)将乙醇与水按1～10∶1～10的体积比混合制得乙醇水溶液，首先在所述乙醇水溶液中加入0.005～0.02g/ml的有机胺混合均匀，制得混合溶液；
2)然后向步骤1)所得混合溶液中加入铁纳米粒，并滴加0.05～0.2g/ml的正硅酸四乙酯；
3)再向步骤2)所得产物中通入6～9MPa的CO2并升温至40～45℃进行化学反应，搅拌反应22～26h，待反应结束后，冷却并放出CO2；
4)将步骤3)所得固体产物水洗干燥后进行高温焙烧，即可得到所述费托合成单分散铁基催化剂。
6.根据权利要求5所述的费托合成单分散铁基催化剂的制备方法，其特征在于：所述步骤4)中，焙烧温度为500～560℃，焙烧时间为4.5～5.5h。
7.根据权利要求5所述的费托合成单分散铁基催化剂的制备方法，其特征在于：所述步骤2)中，铁纳米粒按铁的负载量为5～40wt％加入。
8.一种权利要求1所述费托合成单分散铁基催化剂的应用，其特征在于：将所述费托合成单分散铁基催化剂用于以合成气为原料费托合成α-烯烃，费托合成反应条件为：反应温度为190～360℃，反应压力为0.5～5.0MPa，进气体积空速为400～20000h-1，搅拌转速为400～1400rpm，H2与CO进料体积比为11～3∶1。
9.根据权利要求8所述的费托合成单分散铁基催化剂的应用，其特征在于：所述费托合成单分散铁基催化剂的还原条件为：还原温度为300～500℃，还原压力为0.2～1.2MPa，搅拌转速为400～1400rpm，进气体积空速为400～3500h-1，反应时间为6～18h，纯氢气或合成气氛。
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