CN109261159A - 一种有机硫转化型耐硫变换催化剂及其制备方法 - Google Patents

一种有机硫转化型耐硫变换催化剂及其制备方法 Download PDF

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CN109261159A
CN109261159A CN201811224176.XA CN201811224176A CN109261159A CN 109261159 A CN109261159 A CN 109261159A CN 201811224176 A CN201811224176 A CN 201811224176A CN 109261159 A CN109261159 A CN 109261159A
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纵秋云
匡建平
姚敏
周春丽
郭中山
高辉
刘博男
肖杰飞
黄斌
张晋
刘镓烁
武祥元
古黎明
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Ningxia Shen Yao Technology Co Ltd
QINGDAO LIANXIN CHEMICAL CO Ltd
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Abstract

本发明涉及一种耐硫变换催化剂及制备方法，所述催化剂以镁铝尖晶石为载体，催化剂中有效成分：钴以CoO计为催化剂总量的0.2～20％，钼以MoO3计为催化剂总量的1～30％，添加抑制甲硫醇生成的助剂。催化剂制备方法为浸渍法。本发明在低水/气条件下抑制甲硫醇等硫化物生成的新型助剂，添加该助剂，使催化剂在低水/气条件下具有抑制甲硫醇生成的功能，减轻了后续工段脱硫的负担，保证有机硫化物能够彻底脱除，满足煤化工发展的新需要。

Description

一种有机硫转化型耐硫变换催化剂及其制备方法
技术领域
本发明涉及一种耐硫变换催化剂及其制备方法，具体地涉及一种减少或抑制甲硫醇等有机硫生成的耐硫变换催化剂及其制备方法。
背景技术
钴-钼系变换催化剂由于活性温区宽，具有优异的变换活性和选择性，不存在耐中毒等优点被广泛应用于煤化工生产的变换生产过程，同时该催化剂还具有优异的有机硫水解转化功能。但随着煤化工新技术的开发和节能型低水/气变换新工艺的应用，当工艺气中水/气低降，受化学平衡的影响，有机硫水解反应的转化率将会降低。特别是随着原料煤种的变化，煤气化产生的原料气中还会有微量的硫醇等副产物(如硫醇，硫醚等)带入，这些高分子的硫化物在低水/气工艺在条件下的转化率也会减少，给下游产品净化(低温甲醇洗脱硫)造成困难，影响了节能型低水气变换工艺的推广使用。
申请人的专利CN103495421B中研究了耐硫甲烷化催化剂，但是并未认识到如何在低水/气条件下促进氧硫碳和甲硫醇等硫化物转化。
发明内容
本发现并找出在低水/气条件下促进氧硫碳和甲硫醇等硫化物转化的新型助剂，提高催化剂在低水/气条件下对甲硫醇等硫化物的转化功能，满足煤化工发展的需要。该法制的催化剂甲硫醇生成量明显降低，其对比评价结果如表1所示。
为解决上述技术问题，本发明提供一种有机硫转化型耐硫变换催化剂，所述催化剂中有效成分：钴以CoO计为催化剂总量的0.2～20％，钼以MoO3计为催化剂总量的1～20％，添加有机硫转化助剂，所述助剂的加入量为催化剂总量的0.5-10％重量百分比。所述的有机硫转化助剂为Mn、Zr、K、Na、 Ca、Ti、Fe的氧化物、硝酸盐或硫酸盐或碳酸盐。
所述催化剂以镁铝尖晶石、拟薄水铝石、氧化铝中的任一种或几种的混合物为载体物料。
本发明还要求保护上述的催化剂的制备方法，包括如下步骤：(1)将有机硫转化助剂和载体物料加入胶溶剂进行捏合、挤条并焙烧制得催化剂载体；(2)将含有活性组分钴和钼混合物共浸液浸渍所述的催化剂载体，然后干燥或焙烧制得催化剂。
其中所述胶溶剂是柠檬酸、硝酸、或碱土金属、碱金属中的一种或多种的硝酸盐或/和硫酸盐。
本发明还要求保护上述的催化剂的用途，应用于煤化工生产的变换生产过程，在低水/气条件下促进氧硫碳和甲硫醇等硫化物转化。
本发明还进一步要求保护一种有机硫转化型耐硫变换方法，使用上述的催化剂；反应条件如下：压力3MPa,空速2000H-1，水气0.2，反应温度300℃；有机硫化物生成量低于1.2ppm。
本发明在低水/气条件下抑制甲硫醇等硫化物生成的新型助剂，添加该助剂，使催化剂在低水/气条件下具有抑制甲硫醇生成的功能，减轻了后续工段脱硫的负担，保证有机硫化物能够彻底脱除，满足煤化工发展的新需要。
具体实施方式
现结合实施例进一步说明本发明，但本发明的范围不限于下述实施例。
实施例1
取拟薄水铝石200克，镁铝尖晶石100克，助剂ZrO 10克混合均均匀，加入田菁粉10克，用1％的柠檬酸溶液进行捏合，挤条并于550℃焙烧3小时制得载体。取载体100克，将四钼酸氨12克，硝酸钴90克配成共浸液，将溶液等体积浸渍载体，烘干和/或焙烧制得催化剂。催化剂编号为C-1。其测试结果如表1所示。
实施例2
制备方法同实施例1，不同的是将ZrO 10克换成30克:Zr(OH)2催化剂编号为C-2。其性能对比如表1所示。
实施例3
制备方法同实施例1，不同的是将ZrO 10换成MnO 20克，催化剂编号为 C-3。其性能对比如表1所示。
实施例4
制备方法同实施例1，不同的是将1％的柠檬酸溶液换成5％的硝酸进行捏合，催化剂编号为C-4。其性能对比如表1所示。
表1催化剂甲硫醇生成量对比
实验条件：压力3MPa,空速2000H-1,水气0.2，反应温度300℃
原料气组成：N21.66％；CO 24.56％,CO2 30.82％.H2S 0.1989％,H2余量。

Claims (10)

1.一种有机硫转化型耐硫变换催化剂，其特征在于，所述催化剂中有效成分：钴以CoO计为催化剂总量的0.2～20％，钼以MoO3计为催化剂总量的1～20％，添加有机硫转化助剂，所述助剂的加入量为催化剂总量的0.5-10％重量百分比。
2.根据权利要求1所述的催化剂，其特征在于，所述的有机硫转化助剂为Mn、Zr、K、Na、Ca、Ti、Fe的氧化物、硝酸盐或硫酸盐或碳酸盐。
3.根据权利要求1所述的催化剂，其特征在于，所述催化剂以镁铝尖晶石、拟薄水铝石、氧化铝中的任一种或几种的混合物为载体物料。
4.权利要求1-3任一项所述的催化剂的制备方法，其特征在于，包括如下步骤：(1)将有机硫转化助剂和载体物料加入胶溶剂进行捏合、挤条并焙烧制得催化剂载体；(2)将含有活性组分钴和钼混合物共浸液浸渍所述的催化剂载体，然后干燥或焙烧制得催化剂。
5.根据权利要求4所述的制备方法，其特征在于，所述胶溶剂是柠檬酸、硝酸、或碱土金属、碱金属中的一种或多种的硝酸盐或/和硫酸盐。
6.权利要求1-3任一项所述的催化剂的用途，其特征在于，应用于煤化工生产的变换生产过程，在低水/气条件下促进硫化物转化。
7.根据权利要求7所述的用途，其特征在于，所述硫化物包括氧硫碳和甲硫醇。
8.一种有机硫转化型耐硫变换方法，其特征在于，使用权利要求1-3任一项所述的催化剂。
9.根据权利要求8所述的方法，其特征在于，反应条件如下：压力3MPa,空速2000H-1，水气0.2，反应温度300℃。
10.根据权利要求8所述的方法，其特征在于，有机硫化物生成量低于1.2ppm。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112371132A (zh) * 2020-11-30 2021-02-19 青岛中瑞泰达催化新材料有限公司 一种抑制硫醇低温耐硫变换催化剂及其制备方法和应用

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WO2001074484A2 (en) * 2000-03-31 2001-10-11 The Regents Of The University Of Michigan Transition metal carbides, nitrides and borides and their oxygen containing analogs useful as water gas shift catalysts
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112371132A (zh) * 2020-11-30 2021-02-19 青岛中瑞泰达催化新材料有限公司 一种抑制硫醇低温耐硫变换催化剂及其制备方法和应用

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