CN114950430A - 一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法和应用 - Google Patents
一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明一种蛋黄‑蛋壳结构Fe@ZrO2费托合成催化剂的制备方法和应用，该催化剂制备过程如下：(1)将氯化铁金属前驱体水溶液加入正辛烷和表面活性剂形成混合溶液，搅拌至溶液透明；(2)在透明溶液中加入NaBH4水溶液，搅拌至无气泡产生；(3)所得溶液加入氨水和正硅酸乙酯，搅拌后分离得到固体产物；(4)将所得固体产物分散到无水乙醇溶液中，加入含有表面活性剂的水溶液和正丁醇锆，搅拌后分离并干燥得到固体粉末；(5)将所得固体粉末用碱溶液处理后用水溶液洗涤，干燥并焙烧得到样品。本发明制备的催化剂为蛋黄‑蛋壳结构，有利于改善费托合成过程中反应物和产物的扩散和吸附，形貌和尺寸可调，具有活性位点多，稳定性高，C5+烃类选择性高的优点。
Description
技术领域
本发明涉及催化剂的制备方法和应用，具体涉及一种蛋黄-蛋壳结构 Fe@ZrO2费托合成催化剂的制备方法和应用。
背景技术
目前费托合成Fe基催化剂活性位点少，稳定性差，特定碳链长度的产物选择性不高。
发明内容
为了克服现有费托合成Fe基催化剂存在的缺点，本发明采用微乳液与硬模板相结合的方法，实现蛋黄-蛋壳结构Fe@ZrO2催化材料的合成，并将该材料作为新型纳米催化剂用于费托合成的反应，与传统催化剂相比，该催化剂具有更多的活性位点、更好的反应稳定性以及优良的C5+碳氢化合物选择性。
为了达到上述目的，本发明采用以下技术方案。
一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法，包括以下步骤：
(1)将氯化铁金属前驱体水溶液加入正辛烷和表面活性剂形成的混合溶液，搅拌至溶液透明；
(2)在步骤(1)得到的透明溶液中加入NaBH4水溶液，搅拌至无气泡产生；
(3)在步骤(2)得到的溶液中加入氨水和正硅酸乙酯，搅拌3～12小时，分离得到固体产物；
(4)将步骤(3)得到的固体产物分散到无水乙醇溶液中，加入含有表面活性剂的水溶液和正丁醇锆，搅拌6～12小时，分离并在80～120摄氏度下干燥得到固体粉末；
(5)将步骤(4)得到的固体粉末用碱溶液处理12～72小时，用水溶液洗涤，干燥并在400-1000摄氏度焙烧得到所述Fe@ZrO2费托合成催化剂。
进一步地，所述含铁金属前驱体水溶液为FeCl3水溶液，各物质的用量比例如下：0.1～3mol/L的氯化铁溶液0.5～15mL，正辛烷30～300mL，表面活性剂5～100mL，NaBH40.1～1g，氨水0.5～10mL，正硅酸乙酯1～20mL，乙醇溶液100～1000mL，正丁醇锆1～20mL。
进一步地，上述比例中，氯化铁溶液优选为浓度1mol/L、体积2mL，正辛烷优选为100mL，表面活性剂为Lutensol AO525mL，NaBH4优选为0.5g，氨水优选为2.5mL，正硅酸乙酯优选为5mL，乙醇溶液优选为500mL，正丁醇锆优选为6mL，搅拌速率优选为300rpm，碱溶液优选为1mol/L NaOH溶液。
进一步地，步骤(1)、步骤(2)、步骤(3)和步骤(4)中，搅拌速度为200～400rpm。
上述制备方法制备的蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂为球形颗粒，粒径为5～50nm，优选为10nm；颗粒具有中空介孔结构，该中空纳米颗粒具有多孔结构的ZrO2费托壳层和铁氧化合物内核，内核和壳层中间有空腔；壳层厚度1～10nm，内核直径3～10nm，空腔内径1～50nm，催化剂比表面积100～500m2/g。
本发明制得的蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂可应用在费托合成反应中，其中一种应用方法为：将催化剂填装在固定床反应器中，在压力0.1～ 0.5MPa、温度300～350℃、体积空速1000～3000h-1、摩尔比H2/CO＝0.5～ 3.0的反应条件下，用H2和CO的混合气体还原8～24h，然后在温度260～ 350℃、压力1.5～4.0MPa、体积空速1000～9000h-1、摩尔比H2/CO＝0.5～ 3.0的反应条件下进行费托合成反应，液相产物用冰水浴收集，气相产物通入气相色谱进行分析。
本发明与现有技术相比，具有如下优点：
1、本发明的催化剂具有纳米级的球形中空结构，同时壳层具有丰富孔结构壳层厚度、内核直径和空腔直径可调，有利于改善费托合成过程中反应物和产物的扩散和吸附，可选择性合成特定碳链长度的烃类化合物；
2、本发明的催化剂可显著提高费托合成反应性能，CO转化率最高可达到98％以上，C5+烃类选择性最高可达到60％以上。
附图说明
图1为本发明实施例一中蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的电镜照片；
图2为本发明实施例二中蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的电镜照片；
图3为本发明实施例三中蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的电镜照片。
具体实施方式
以下仅为本发明的较佳实施例，不能以此限定本发明的范围。凡依本发明申请专利范围所作的均等变化与修饰，皆应仍属于本发明专利涵盖的范围内。
实施例1
量取100mL正辛烷和25mL Lutensol AO5于500mL是圆底烧瓶，随后加入浓度为0.5mol/L的氯化铁溶液体积2mL，搅拌至透明，加入0.5g NaBH4，搅拌5小时，加入2.5mL氨水和5mL正硅酸乙酯，搅拌8小时，离心分离收集固体产物，将固体产物超声分散于500mL无水乙醇溶液，加入2mL Lutensol AO5和6mL正丁醇锆，搅拌12小时，离心分离得到固体粉末，将固体粉末在110℃下干燥12小时后分散于1mol/L的NaOH溶液，静置3小时，所得产物用去离子水洗涤5次以上，在110℃下干燥12小时，随后在马弗炉中550℃焙烧6小时得到催化剂1#。
称取催化剂1#和石英砂各0.2g混合填装到50mL固定床反应器中。还原条件为：温度320℃、压力0.1MPa、空速1000h-1、合成气(H2/CO＝1.0)10h。反应条件为温度280℃、压力2.0MPa、空速5000h-1、H2/CO＝1.0，用冷阱收集液相产物，尾气和液相产物用气相色谱进行分析，分析结果列于表1。
实施例2
量取100mL正辛烷和25mL Lutensol AO5于500mL是圆底烧瓶，随后加入浓度为2mol/L的氯化铁溶液体积2mL，搅拌至透明，加入0.8g NaBH4，搅拌5小时，加入3.0mL氨水和5mL正硅酸乙酯，搅拌8小时，离心分离收集固体产物，将固体产物超声分散于500mL无水乙醇溶液，加入2mL Lutensol AO5和6mL正丁醇锆，搅拌12小时，离心分离得到固体粉末，将固体粉末在110℃下干燥12小时后分散于1mol/L的NaOH溶液，静置3小时，所得产物用去离子水洗涤5次以上，在110℃下干燥12小时，随后在马弗炉中550℃焙烧6小时得到催化剂2#。
称取催化剂2#和石英砂各0.2g混合填装到50mL固定床反应器中。还原条件为：温度320℃、压力0.1MPa、空速1000h-1、合成气(H2/CO＝ 1.0)10h。反应条件为温度280℃、压力3.0MPa、空速2000h-1、H2/CO＝2.0，用冷阱收集液相产物，尾气和液相产物用气相色谱进行分析，分析结果列于表1。
实施例3
量取80mL正辛烷和30mL Lutensol AO5于500mL是圆底烧瓶，随后加入浓度为1.5mol/L的氯化铁溶液体积4mL，搅拌至透明，加入1.2g NaBH4，搅拌8小时，加入3.0mL氨水和10mL正硅酸乙酯，搅拌8小时，离心分离收集固体产物，将固体产物超声分散于500mL无水乙醇溶液，加入2mL Lutensol AO5和7mL正丁醇锆，搅拌12小时，离心分离得到固体粉末，将固体粉末在110℃下干燥12小时后分散于1mol/L的NaOH溶液，静置3小时，所得产物用去离子水洗涤5次以上，在110℃下干燥12小时，随后在马弗炉中750℃焙烧6小时得到催化剂3#。
称取催化剂3#和石英砂各0.2g混合填装到50mL固定床反应器中。还原条件为：温度320℃、压力0.1MPa、空速2000h-1、合成气(H2/CO＝ 1.0)12h。反应条件为温度280℃、压力2.0MPa、空速4500h-1、H2/CO＝1.0，用冷阱收集液相产物，尾气和液相产物用气相色谱进行分析，分析结果列于表1。
对比例1
购买商业ZrO2载体4.0g，，在750℃下煅烧3h，除去载体中的杂质。然后将2.4g Fe(NO3)3·9H2O配置成1mol/L的硝酸铁溶液浸渍在处理过的ZrO2载体上，浸渍完成后在110℃的条件下干燥12h。最后在750℃条件下焙烧5h，得到Fe/ZrO2催化剂4#。
称取催化剂4#和石英砂各0.2g混合填装到50mL固定床反应器中。还原条件为：温度320℃、压力0.1MPa、空速2000h-1、合成气(H2/CO＝1.0)12h。反应条件为温度280℃、压力2.0MPa、空速4500h-1、H2/CO＝1.0，用冷阱收集液相产物，尾气和液相产物用气相色谱进行分析，分析结果列于表1。
通过实施例、对比例以及图1-图3可以看出，通过改变合成条件可以调节蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的形貌和尺寸，显著影响费托合成催化反应性能。优选的蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂可使费托合成反应活性达到95％以上，C5+烃类选择性可达到60％以上，C5-12汽油馏分段产物可达到45％以上。
Claims (6)
1.一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法，其特征在于，包括以下步骤：
(1)将氯化铁金属前驱体水溶液加入正辛烷和表面活性剂形成的混合溶液，搅拌至溶液透明；
(2)在步骤(1)得到的透明溶液中加入NaBH4水溶液，搅拌至无气泡产生；
(3)在步骤(2)得到的溶液中加入氨水和正硅酸乙酯，搅拌3～12小时，分离得到固体产物；
(4)将步骤(3)得到的固体产物分散到无水乙醇溶液中，加入含有表面活性剂的水溶液和正丁醇锆，搅拌6～12小时，分离并在80～120摄氏度下干燥得到固体粉末；
(5)将步骤(4)得到的固体粉末用碱溶液处理12～72小时，用水溶液洗涤，干燥并在400-1000摄氏度焙烧得到所述Fe@ZrO2费托合成催化剂。
2.如权利要求1所述一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法，其特征在于，所述含铁金属前驱体水溶液为FeCl3水溶液，各物质的用量比例如下：0.1～3mol/L的氯化铁溶液0.5～15mL，正辛烷30～300mL，表面活性剂5～100mL，NaBH40.1～1g，氨水0.5～10mL，正硅酸乙酯1～20mL，乙醇溶液100～1000mL，正丁醇锆1～20mL。
3.如权利要求1所述一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法，其特征在于，步骤(1)、步骤(2)、步骤(3)和步骤(4)中，搅拌速度为200～400rpm。
4.如权利要求1所述一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法，其特征在于，步骤(5)中，碱溶液为NaOH溶液、KOH溶液或Na2CO3溶液。
5.一种采用权利要求1～4任一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的制备方法制得的蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的应用，其特征在于，在反应温度260～350℃、压力1.5～4.0MPa、体积空速1000～9000h-1、摩尔比H2/CO＝0.5～3.0的反应条件下，进行费托合成反应。
6.如权利要求5所述一种蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂的应用其特征在于，所述蛋黄-蛋壳结构Fe@ZrO2费托合成催化剂在催化反应前，在压力0.1～0.5MPa、温度300～350℃、体积空速1000～3000h-1、摩尔比H2/CO＝0.5～3.0的条件下用合成气还原8～24h。
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