CN110560071A - 一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法 - Google Patents
一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法,其制备的催化剂可应用到二氧化碳加氢制甲醇上。该方法包括以下步聚:(1)蔗糖中加入去离子水,室温下搅拌至其完全溶解,于160‑220℃反应8‑24h;(2)将所得悬浊液进行离心分离,置于80‑120℃烘箱干燥24h或以上时间;(3)取上述步骤(2)中干燥所得不溶物加入乙二醇溶液进行溶解,向溶液中加入前驱体,得到前驱体悬浊液;(4)将前驱体悬浊液进行离心分离并干燥;(5)将干燥后的产品在空气中进行焙烧3‑5小时;(6)将焙烧所得产品在200‑400℃下于氢气流中还原1‑3h,得到无载体二氧化碳加氢制甲醇空心球催化剂。
Description
技术领域
本发明涉及一种催化剂制备方法,更具体地说涉及一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法。
背景技术
甲醇是一种重要的化工中间体,同时是理想的液体燃料添加剂,工业上对其需求量非常大,二氧化碳加氢制甲醇工艺是工业甲醇的重要来源之一,同时可以极大提高碳原子的利用率。现代化工业的迅速发展和人类生活方式的巨大改变加剧了化学燃料的燃烧和大气中二氧化碳的积累,温室效应的影响日益显著。如何有效利用二氧化碳,减少其排放,实现绿色经济和可持续发展是亟待解决的重要问题。工业上常以二氧化碳为原料,利用二氧化碳与氢气的反应将其转化成甲醇、甲酸等重要有机化工原料,实现二氧化碳减排,其中甲醇可以作为生产甲醛乙酸和生物柴油的原料,是有机化工的重要物料。
二氧化碳反应活性非常低,工业上常用负载型铜基催化剂催化二氧化碳加氢,通常以Al2O3、ZrO2、SiO2、TiO2等多孔材料为载体,负载活性组分铜和氧化锌。常用的制备方法有浸渍法、沉积沉淀法、化学气相沉积法和离子交换法等。(1)浸渍法将适量载体浸渍于含有活性组分的溶液中,浸渍平衡后,除去剩余液体,再经干燥、焙烧、活化等程序即可制得催化剂。(2)沉积沉淀法在活性金属组分与其载体充分接触的前提下,引入沉淀剂进行沉淀,使金属活性组分沉淀于载体的内孔或表面。(3)化学气相沉积法利用气相反应,在特定沉积温度和足够高的蒸汽压下,将活性组分以气态形式引入到待沉积固态载体薄膜上,实现活性组分的负载与分散。(4)离子交换法利用载体表面上存在的可交换离子,将活性组分通过离子交换负载到载体上,实现活性组分的可控引入,然后经洗涤、干燥、焙烧等处理制得催化剂。
上述负载型催化剂的制备过程中,浸渍法活性组分含量不易控制,浸渍溶液浓度过低时,负载活性组分在孔内分散不均匀且结构稳定性差,催化性能不稳定;浸渍溶液浓度过高时,离子易团聚,催化活性有限,为了寻找最佳合适条件,需要进行多次重复性实验,费时费力;且在煅烧过程中活性组分易烧结,丧失催化活性。沉积沉淀法中,活性组分的负载情况难以调变控制,重复性差,成核过程更易于发生在溶液中,且生成的金属颗粒较大,比表面积小。化学气相沉积法对仪器和操作条件要求较高,且操作过程繁琐,不易推广进行。离子交换法中金属与载体的相互作用较弱,产生的活性组分含量有限,适用范围较小。综上所述,传统方法很难实现活性组分在载体上的高度分散,活性位点较难调控。因此需要开发一种二氧化碳加氢制甲醇用催化剂的制备方法,提升二氧化碳制甲醇的转化率和选择性。
发明内容
本发明的目的是解决现有技术中存在的问题与不足,提供一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法,该方法制备的催化剂为无载体、高比表面积铜-氧化锌空心球催化剂,可应用到二氧化碳加氢制甲醇上。此方法可利用碳球模板形成形状大小均一且粒径可调的铜-氧化锌混合物空心球,通过构造有效组分的较高的内比表面积,实现了活性组分的良好分散,使催化剂摆脱了载体存在的限制,且活性组分不因催化过程而团聚失活,提高了催化剂的催化效率和使用寿命,并显著提升了二氧化碳制甲醇的转化率和选择性。
本发明通过以下技术方案实现:
本发明的无载体二氧化碳加氢制甲醇空心球催化剂的制备方法,其包括以下步聚:
(1)称取蔗糖于烧杯中,加入去离子水,室温下搅拌至其完全溶解,将所得透明溶液转移到聚四氟乙烯衬里的水热釜中,密封后放进烘箱,于160-220℃反应8-24h;
(2)将上述水热反应所得悬浊液进行离心分离,用水和乙醇分别洗涤所得不溶物3-5次,置于80-120℃烘箱干燥24h或以上时间;
(3)取上述步骤(2)中干燥所得不溶物放入三口烧瓶中,同时加入乙二醇溶液进行溶解,超声分散均匀后,向溶液中加入前驱体,回流加热至100-140℃,高速搅拌8-14h,得到混合组分催化剂的前驱体悬浊液;
(4)将上述搅拌后的前驱体悬浊液进行离心分离,所得产物用水和乙醇分别洗涤两次后置于80-120℃烘箱中干燥24h或以上时间;
(5)将上述步骤(4)干燥后的产品在450-600℃下于空气中进行焙烧3-5小时;
(6)将焙烧所得产品放入管式炉,在200-400℃下于氢气流中还原1-3h,得到无载体二氧化碳加氢制甲醇空心球催化剂。
本发明上述的制备方法,其进一步的技术方案是所述的前驱体为硝酸铜和硝酸锌混合物,硝酸铜和硝酸锌摩尔比为7:3-3:7。
本发明与现有技术相比具有以下有益效果:
本发明的方法制得的催化剂经扫描电子显微镜拍摄,形状大小均一,呈现为粒径200-300nm左右的空心球形,分布均匀,高倍透射电镜拍摄图片进一步说明其为空心小球,BET测试法显示其比表面积高达250m2/g,X-射线衍射检测结果表明铜锌组分混合均匀,所得催化剂晶型较好,证明制备成功。利用二氧化碳加氢反应测试其活性,结果表明其产物选择性高达90%,甲醇产率为87%。利用此方法制备的催化剂回收率可达百分之百,重复性高,并且操作简便,可进行大量生产。所得产品分散度高,活性组分混合均匀,提高了二氧化碳加氢的催化效率和产物选择性,达到本发明的目的。
本发明制得的催化剂无需载体支撑,自身拥有超高比表面积度的活性组分,独特的空心球结构使其拥有较大的比表面积,煅烧过程中活性组分不易烧结,催化效率显著提高,且制备过程无毒无害,操作简便。
具体实施方式
通过下述实施例,对本发明作进一步的详细说明,但不应将此理解为本发明上述主题的范围仅限于以下的实例。
实施例1
无载体二氧化碳加氢制甲醇空心球催化剂的制备方法、操作条件以及催化剂的性能指标和催化效果:
1、催化剂的制备:
(1)称取5g蔗糖于烧杯中,加入60mL去离子水,室温下搅拌至其完全溶解,将所得透明溶液转移到聚四氟乙烯衬里的水热釜中,密封后放进烘箱,于160℃反应8h;
(2)将上述水热反应所得悬浊液进行离心分离,用水和乙醇分别洗涤所得不溶物3次,置于80℃烘箱干燥24h;
(3)取0.1g上述步骤干燥所得产品放入三口烧瓶中,同时加入60mL乙二醇溶液进行溶解,超声分散均匀后,向溶液中加入摩尔比为1:1的硝酸铜和硝酸锌,回流加热至100℃,以600rpm的转速搅拌8h,得到混合组分催化剂的前驱体悬浊液;
(4)将上述搅拌后的溶液进行离心分离,所得产物用水和乙醇分别洗涤两次后置于80℃烘箱中干燥24h;
(5)将上述步骤干燥后的产品在450℃下于空气中进行焙烧3小时;
(6)将焙烧所得产品放入管式炉,在250℃下于氢气流中还原1h,得到无载体高比表面积铜-氧化锌的二氧化碳加氢制甲醇用空心球催化剂。密封保存待使用。
2、催化剂的性能指标和催化效果:
利用此方法制备的高比表面积铜-氧化锌空心球催化剂比表面积为242m2/g,活性组分混合均匀,透射电子显微镜显示其平均粒径为300nm。以TPD作为固定床反应器,称取0.05g样品置于U形管,初始阶段通入氩气进行吹扫,升温至250℃后,以25mL/min的流速通入质量比为1:7.27的氢气和二氧化碳混合气,质谱检测结果表明流速二氧化碳的转化率达到97%,甲醇的选择性高达85%,主要有效产物为甲醇和甲酸。相比其他制备方法获得的催化剂,本方法制备的催化剂催化活性更好、选择性更高。连续通入反应气体24h,甲醇转化率和选择性未见明显下降,证明催化剂使用寿命理想。
实施例2
无载体二氧化碳加氢制甲醇空心球催化剂的制备方法、操作条件以及催化剂的性能指标和催化效果:
1、催化剂的制备:
(1)称取10g蔗糖于烧杯中,加入100mL去离子水,室温下搅拌至其完全溶解,将所得透明溶液转移到聚四氟乙烯衬里的水热釜中,密封后放进烘箱,于180℃反应16h;
(2)将上述水热反应所得悬浊液进行离心分离,用水和乙醇分别洗涤所得不溶物3次,置于80℃烘箱干燥24h;
(3)取0.2g上述步骤干燥所得产品放入三口烧瓶中,同时加入100mL乙二醇溶液进行溶解,超声分散均匀后,向溶液中加入摩尔比为7:3的硝酸铜和硝酸锌,回流加热至120℃,以600rpm的转速搅拌12h,得到混合组分催化剂的前驱体悬浊液;
(4)将上述搅拌后的溶液进行离心分离,所得产物用水和乙醇分别洗涤两次后置于80℃烘箱中干燥24h;
(5)将上述步骤干燥后的产品在500℃下于空气中进行焙烧3小时;
(6)将焙烧所得产品放入管式炉,在300℃下于氢气流中还原1.5h,得到无载体高比表面积铜-氧化锌的二氧化碳加氢制甲醇用空心球催化剂。密封保存待使用。
2、催化剂的性能指标和催化效果:
利用此方法制备的高比表面积铜-氧化锌空心球催化剂比表面积为250m2/g,活性组分混合均匀,透射电子显微镜显示其平均粒径为200nm。以TPD作为固定床反应器,称取0.05g样品置于U形管,初始阶段通入氩气进行吹扫,升温至250℃后,以25mL/min的流速通入质量比为1:7.27的氢气和二氧化碳混合气,质谱检测结果表明流速二氧化碳的转化率达到100%,甲醇的选择性高达87%,主要有效产物为甲醇和甲酸。相比其他制备方法获得的催化剂,本方法制备的催化剂催化活性更好、选择性更高。连续通入反应气体24h,甲醇转化率和选择性未见明显下降,证明催化剂使用寿命理想。
实施例3
无载体二氧化碳加氢制甲醇空心球催化剂的制备方法、操作条件以及催化剂的性能指标和催化效果:
1、催化剂的制备:
(1)称取10g蔗糖于烧杯中,加入100mL去离子水,室温下搅拌至其完全溶解,将所得透明溶液转移到聚四氟乙烯衬里的水热釜中,密封后放进烘箱,于220℃反应24h;
(2)将上述水热反应所得悬浊液进行离心分离,用水和乙醇分别洗涤所得不溶物3次,置于80℃烘箱干燥24h;
(3)取0.1g上述步骤干燥所得产品放入三口烧瓶中,同时加入100mL乙二醇溶液进行溶解,超声分散均匀后,向溶液中加入摩尔比为3:7的硝酸铜和硝酸锌,回流加热至140℃,以600rpm的转速搅拌16h,得到混合组分催化剂的前驱体悬浊液;
(4)将上述搅拌后的溶液进行离心分离,所得产物用水和乙醇分别洗涤两次后置于80℃烘箱中干燥24h;
(5)将上述步骤干燥后的产品在600℃下于空气中进行焙烧3小时;
(6)将焙烧所得产品放入管式炉,在350℃下于氢气流中还原3h,得到无载体高比表面积铜-氧化锌的二氧化碳加氢制甲醇用空心球催化剂。密封保存待使用。
2、催化剂的性能指标和催化效果:
利用此方法制备的高比表面积铜-氧化锌空心球催化剂比表面积为230m2/g,活性组分混合均匀,透射电子显微镜显示其平均粒径为240nm。以TPD作为固定床反应器,称取0.05g样品置于U形管,初始阶段通入氩气进行吹扫,升温至250℃后,以25mL/min的流速通入质量比为1:7.27的氢气和二氧化碳混合气,质谱检测结果表明流速二氧化碳的转化率达到95%,甲醇的选择性高达84%,主要有效产物为甲醇和甲酸。相比其他制备方法获得的催化剂,本方法制备的催化剂催化活性更好、选择性更高。连续通入反应气体24h,甲醇转化率和选择性未见明显下降,证明催化剂使用寿命理想。
Claims (2)
1.一种无载体二氧化碳加氢制甲醇空心球催化剂的制备方法,其特征在于包括以下步聚:
(1)称取蔗糖于烧杯中,加入去离子水,室温下搅拌至其完全溶解,将所得透明溶液转移到聚四氟乙烯衬里的水热釜中,密封后放进烘箱,于160-220℃反应8-24h;
(2)将上述水热反应所得悬浊液进行离心分离,用水和乙醇分别洗涤所得不溶物3-5次,置于80-120℃烘箱干燥24h或以上时间;
(3)取上述步骤(2)中干燥所得不溶物放入三口烧瓶中,同时加入乙二醇溶液进行溶解,超声分散均匀后,向溶液中加入前驱体,回流加热至100-140℃,高速搅拌8-14h,得到混合组分催化剂的前驱体悬浊液;
(4)将上述搅拌后的前驱体悬浊液进行离心分离,所得产物用水和乙醇分别洗涤两次后置于80-120℃烘箱中干燥24h或以上时间;
(5)将上述步骤(4)干燥后的产品在450-600℃下于空气中进行焙烧3-5小时;
(6)将焙烧所得产品放入管式炉,在200-400℃下于氢气流中还原1-3h,得到无载体二氧化碳加氢制甲醇空心球催化剂。
2.根据权利要求1所述的制备方法,其特征在于所述的前驱体为硝酸铜和硝酸锌混合物,硝酸铜和硝酸锌摩尔比为7:3-3:7。
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