CN107376937B - 一种有序介孔复合催化剂及其制备方法和应用 - Google Patents

一种有序介孔复合催化剂及其制备方法和应用 Download PDF

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CN107376937B
CN107376937B CN201710691620.8A CN201710691620A CN107376937B CN 107376937 B CN107376937 B CN 107376937B CN 201710691620 A CN201710691620 A CN 201710691620A CN 107376937 B CN107376937 B CN 107376937B
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雷廷宙
陈高峰
王志伟
林鹿
何晓峰
关倩
李学琴
朱金陵
杨延涛
徐海燕
董莉莉
辛晓菲
杨淼
李自杰
石杰
赵宝珠
韩刚
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Energy Research Institute Co Ltd of Henan Academy of Sciences
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Abstract

本发明属于生物质能源利用技术领域，具体涉及一种用于生物质合成气制备低碳醇的有序介孔复合催化剂及其制备方法和应用。所述催化剂以有序介孔C‑ZrO2为载体，载体上负载有活性组分和助剂；其中，所述的活性组分为Cu和M，M为选自Ni、Co、Fe中的至少一种；所述的助剂为贵金属N以及碱金属或碱土金属A。采用本发明的催化剂，可以解决以往用于生物质合成气制备低碳醇的该类催化剂CO加氢转化率低，产物中低碳醇尤其是乙醇选择性低的问题。

Description

一种有序介孔复合催化剂及其制备方法和应用
技术领域
本发明属于生物质能源利用技术领域，具体涉及一种用于生物质合成气制备低碳醇的有序介孔复合催化剂及其制备方法和应用。
背景技术
随着化石能源的日益枯竭和环境污染的日渐加重，开发以生物质能资源为基础的可再生能源有重要的现实价值。以生物质气化后的合成气(H2+CO)为原料经催化转化制备低碳醇(C1-C5正构和异构醇)是生物质能资源制备基础化工原料和清洁燃料添加剂的关键过程。低碳醇是化工能源领域重要的基础原料之一，也是一种优质的动力燃料，更是一种高辛烷值、低污染的车用燃料添加剂，是环境友好燃料，已被证实可与汽油混合配成醇-油混合动力燃料。合成气制备低碳醇的反应常伴随着烃类、CO2等副产物的生成，如何提高催化剂的活性和低碳醇的选择性以提高生产过程的效率，成为制约低碳醇合成工艺实用化和工业化的技术瓶颈。
目前常用的合成气制备低碳醇的催化剂有：
(1)以铑基为代表的贵金属催化剂，这一类催化剂具备很高的加氢活性，但价格昂贵，且催化剂易中毒，难以工业化应用；
(2)Dow化学公司开发的硫化钼催化剂，操作条件温和，产物中C2+醇含量高，但对原料气的氢碳比要求苛刻，且产物中CO2含量高；
(3)改性的甲醇合成催化剂，这类催化剂是由甲醇合成催化剂改性而得，其催化活性较高，主要产物为甲醇和异丁醇，但反应条件需要高温(350-450℃)高压(12-16MPa)，且产物中含水量高；
(4)改性的费托CuCo体系催化剂，由于反应条件温和、活性高、主要产物是直链正构醇，具备较强的抗老化、抗毒化能力，碳链增长能力强被认为是最具有工业应用前景的催化剂之一。其储量丰富，价格适中，但单独采用CuCo体系催化剂活性有限，低碳醇的选择性低，因此可作为低碳醇合成催化剂的主要活性成分，通过对CuCo基催化剂进行改性修饰可以极大地提高其催化活性和低碳醇的选择性。
发明内容
本发明的目的是克服现有催化剂体系的不足，提供一种具有更高CO加氢转化率和低碳醇选择性的有序介孔复合催化剂。
为解决上述技术问题，本发明采用的技术方案如下：
一种有序介孔复合催化剂，所述催化剂以有序介孔C-ZrO2为载体，载体上负载有活性组分和助剂；
其中，所述的活性组分为Cu和M，M为选自Ni、Co、Fe中的至少一种；
所述的助剂为贵金属N以及碱金属或碱土金属A。
助剂N为Ru、Rh、Pd、Pt、Ga中的至少一种。
所述载体的比表面积为180-460m2/g，平均孔径4-10nm。
所述催化剂的重量百分组成为Cu：1-20％，M：1-20％，N：0.1-5％，A：0.5-5％，其余为载体。
优选的，所述催化剂的重量百分组成为Cu：3-10％，M：3-10％，N：1-2％，A：1-5％，其余为载体。
本发明进一步提供了一种所述有序介孔复合催化剂的制备方法，以介孔C-ZrO2为载体，采用饱和浸渍法负载Cu、M、N、A组分，经过干燥、焙烧获得催化剂。
其中，将三嵌段共聚物和稀酸催化剂溶解在乙醇中，加入酚醛树脂和氧氯化锆，搅拌，经过铺膜、交联、焙烧获得有序介孔C-ZrO2。
负载Cu、M组分时采用其对应的硝酸盐溶液进行浸渍，负载N组分时优选其氯化物溶液，负载A时优选乙酸钾溶液。
进一步，浸渍时间为12-24h。
进一步，于空气中100-140℃干燥10-28h，于280-550℃焙烧4-8h。
具体的，本发明制备方法包括如下步骤：
1)采用溶剂蒸发诱导自组装法制备比表面积180-460m2/g，平均孔径4-10nm的介孔C-ZrO2载体：将三嵌段共聚物和稀酸催化剂溶解在乙醇中，加入酚醛树脂和氧氯化锆，搅拌，经过铺膜、交联、焙烧获得有序介孔C-ZrO2；
2)采用饱和浸渍法用溶有Cu、M、N以及A的硝酸盐的混合溶液浸渍步骤1)制得的催化剂载体，经过干燥、焙烧获得催化剂。
所述有序介孔复合催化剂在生物质合成气制备低碳醇上有很好的应用。
本发明具有以下特点：①由于催化剂载体采用了高比表面积和平均孔径在4-10nm的有序介孔材料，相对较大的孔道保证了活性组分的高分散性且促进了反应物与产物在孔内的扩散，减轻传质阻力；
②ZrO2同时具备酸性和碱性、氧化性和还原性，为催化剂提供酸性位和原位位点，且介孔碳与二氧化锆复合能有效增加纯介孔碳材料的孔径；
③N助剂的添加能够有效提高混合醇的选择性，且Cu-M-N相互作用，发挥了金属催化剂的协同作用；
④碱金属或碱土金属A助剂的添加，可以中和催化剂的表面酸性，从而抑制醇的脱水反应以及积碳的形成。
本发明与现有技术相比，具有如下优点：
采用本发明的催化剂，可以解决以往用于生物质合成气制备低碳醇的该类催化剂CO加氢转化率低，产物中低碳醇尤其是乙醇选择性低的问题。
附图说明
图1为载体C-ZrO2的TEM透射电镜图谱；
图2为载体C-ZrO2的氮气吸脱附等温线；
图3为载体C-ZrO2的孔径分布曲线图。
具体实施方式
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：
实施例1
一种有序介孔复合催化剂，制备步骤如下：
①在40℃下，将1.0g三嵌段共聚物F127溶解在8.0g乙醇中，加入0.9g稀盐酸(0.2M)，搅拌，加入3.2g氧氯化锆和0.8g可溶性酚醛树脂的乙醇溶液，继续搅拌。将溶液铺膜静置挥发溶剂，100℃聚合交联24h。之后将材料研磨成粉，氮气气氛下500℃焙烧5h，即得有序介孔载体C-ZrO2；
②取步骤①所获得的载体44.3g浸渍于溶有9.5g硝酸铜(Cu(NO3)2·3H2O)、12.4g硝酸钴(Co(NO3)2·6H2O)、0.3g氯化钌(RuCl2·3H2O)以及1.3g乙酸钾(CH3COOK)的混合溶液30ml中，于室温下浸渍14h，之后在空气中110℃干燥12h，再于450℃下焙烧5h，制得所述催化剂A。
催化剂A的重量百分组成如下：Cu 5％，Co5％，Ru0.3％，K1％，余量为介孔载体C-ZrO2。
实施例2
一种有序介孔复合催化剂，制备步骤如下：
①在42℃下，将1.2g三嵌段共聚物P123溶解在10.0乙醇中，加入1.1g0.2mol/l的稀盐酸，搅拌，加入3.4g氧氯化锆和0.9g可溶性酚醛树脂的乙醇溶液，继续搅拌。将溶液铺膜静置挥发溶剂，105℃聚合交联28h。将材料研磨成粉，氮气气氛下550℃焙烧4h，即得有序介孔载体C-ZrO2；
②取步骤①所获得的载体43.8g浸渍于溶有9.5g硝酸铜(Cu(NO3)2·3H2O)、15.3g硝酸铁(Fe(NO3)3·9H2O)、0.5g氯化钌(RuCl2·3H2O)以及2.6g乙酸钾(CH3COOK)混合溶液40ml中，于室温下浸渍16h，在110℃空气中干燥14h，再于480℃温度下焙烧5h，制得催化剂B；
催化剂B的重量百分组成如下：Cu5％，Fe5％，Ru0.5％，K2％，余量为介孔载体C-ZrO2。
实施例3
一种有序介孔复合催化剂，制备步骤如下：
①在40℃下，将1.0g三嵌段共聚物F127溶解在10.0乙醇中，加入0.9g0.2mol/l的稀盐酸，搅拌，加入2.8g氧氯化锆和0.8g可溶性酚醛树脂的乙醇溶液，继续搅拌。将溶液铺膜静置挥发溶剂，105℃聚合交联24h。将材料研磨成粉，氮气气氛下600℃焙烧3h，即得有序介孔载体C-ZrO2；
②取步骤①所获得的载体49g浸渍于溶有9.5g硝酸铜(Cu(NO3)2·3H2O)、12.4g硝酸镍(Ni(NO3)2·6H2O)、0.7g氯化钯(PdCl2)以及1.3g乙酸钾(CH3COOK)混合溶液30ml中，于室温下浸渍14h，在110℃空气中干燥12h，再于450℃温度下焙烧5h，制得催化剂C；
催化剂C的重量百分组成如下：Cu 5％，Ni 5％，Pd 0.2％，K含量为1％，余量为介孔载体C-ZrO2。
实施例4
一种有序介孔复合催化剂，制备步骤如下：
①在40℃下，将1.5g三嵌段共聚物P123溶解在20.0乙醇中，加入2.2g0.3M的稀盐酸，搅拌，加入4.1g氧氯化锆和1.2g可溶性酚醛树脂的乙醇溶液，继续搅拌。将溶液铺膜静置挥发溶剂，100℃聚合交联20h。将材料研磨成粉，氮气气氛下500℃焙烧5h，即得有序介孔载体C-ZrO2。
②取步骤①所获得的载体50g浸渍于溶有19.0g硝酸铜(Cu(NO3)2·3H2O)、12.4g硝酸钴(Co(NO3)2·6H2O)、0.4g硝酸镓(Ga(NO3)2)以及3.9g乙酸钾(CH3COOK)混合溶液30ml，于室温下浸渍14h，在110℃空气中干燥12h，再于450℃温度下焙烧5h，制得催化剂D；
催化剂D的重量百分组成如下：Cu10％，Co5％，Ga0.2％，K3％，余量为介孔载体C-ZrO2。
实施例5
一种有序介孔复合催化剂，制备步骤如下：
①在42℃下，将3.0g三嵌段共聚物F127溶解在30.5乙醇中，加入5.4g0.1M的稀盐酸，搅拌，加入3.2g氧氯化锆和0.8g可溶性酚醛树脂的乙醇溶液，继续搅拌。将溶液铺膜静置挥发溶剂，103℃聚合交联22h。将材料研磨成粉，氮气气氛下580℃焙烧5h，即得有序介孔载体C-ZrO2。
②取步骤①所获得的载体49g浸渍于溶有9.5g硝酸铜(Cu(NO3)2·3H2O)、30.6g硝酸铁(Fe(NO3)3·9H2O)、0.3g氯化铑(RhCl3·3H2O)以及5.2g乙酸钾(CH3COOK)混合溶液30ml，于室温下浸渍14h，在110℃空气中干燥12h，再于450℃温度下焙烧5h，制得催化剂E。
催化剂E的重量百分组成如下：Cu 5％，Fe 10％，Rh 0.2％，K 4％，余量为介孔载体C-ZrO2。
对比例1
按照用于合成气制低碳醇的催化剂及其制备方法(200910057823.7)实施例3的制备方法制备催化剂A1。
对比例2
按照用于合成气制低碳醇的催化剂及其制备方法(200910057823.7)实施例5的制备方法制备催化剂B1。
效果例
①取上述实施例1-5的催化剂A、B、C、D、E以及对比例的催化剂A1和B1各8g用氢气在固定床中还原，还原条件：300℃，常压，恒温12h，2.0L/g.cat.h。
②反应在固定床反应器中进行，反应条件为：300℃，4.0MPa，2.0L/g.cat.h，原料气组成为V(H2)/V(CO)/V(N2)＝60/30/10。反应4h后对所得的产物由气相色谱仪分析，结果见表1。由表可知：该催化剂具有更高的CO加氢催化活性以及低碳醇选择性。
表1

Claims (8)

1.一种用于生物质合成气制备低碳醇的有序介孔复合催化剂，其特征在于，所述催化剂以有序介孔C-ZrO2为载体，载体上负载有活性组分和助剂；
其中，所述的活性组分为Cu和M，M为选自Ni、Co、Fe中的至少一种；
所述的助剂为贵金属N，以及碱金属或碱土金属A；
所述催化剂的重量百分组成为Cu：1-20%，M：1-20%，N：0.1-5%，A：0.5-5%，其余为载体；
所述载体的比表面积为180-460m2/g，平均孔径4-10nm。
2.如权利要求1所述的用于生物质合成气制备低碳醇的有序介孔复合催化剂，其特征在于，所述催化剂的重量百分组成为Cu：3-10%，M：3-10%，N：1-2%，A：1-5%，其余为载体。
3.如权利要求1所述的用于生物质合成气制备低碳醇的有序介孔复合催化剂，其特征在于，贵金属N为Ru、Rh、Pd、Pt中的至少一种。
4.权利要求1-3任一所述用于生物质合成气制备低碳醇的有序介孔复合催化剂的制备方法，其特征在于，以介孔C-ZrO2为载体，采用饱和浸渍法负载Cu、M、N、A组分，经过干燥、焙烧获得催化剂；其中，将三嵌段共聚物和稀酸催化剂溶解在乙醇中，加入酚醛树脂和氧氯化锆，搅拌，经过铺膜、交联、焙烧获得有序介孔C-ZrO2。
5.如权利要求4所述的用于生物质合成气制备低碳醇的有序介孔复合催化剂的制备方法，其特征在于，负载Cu、M组分时采用其对应的硝酸盐溶液进行浸渍。
6.如权利要求5所述的用于生物质合成气制备低碳醇的有序介孔复合催化剂的制备方法，其特征在于，浸渍时间为12-24h。
7.如权利要求4所述的用于生物质合成气制备低碳醇的有序介孔复合催化剂的制备方法，其特征在于，于空气中100-140℃干燥10-28h，于280-550℃焙烧4-8h。
8.权利要求1-3任一所述有序介孔复合催化剂在生物质合成气制备低碳醇上的应用。
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