CN105413446B - 一种固态脱硫剂 - Google Patents

一种固态脱硫剂 Download PDF

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CN105413446B
CN105413446B CN201510898674.2A CN201510898674A CN105413446B CN 105413446 B CN105413446 B CN 105413446B CN 201510898674 A CN201510898674 A CN 201510898674A CN 105413446 B CN105413446 B CN 105413446B
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coordination polymer
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desulphurizing agents
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张晨
邓长胜
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Hebei Thousand Czechs Chemical Technology Co Ltd
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

本发明涉及脱硫剂,具体涉及一种固态脱硫剂。一种固态脱硫剂,由如下重量份数的组分组成:氧化钙3~9份;三氧化二铁5~16份;氟化钙5~10份;氧化铝1~6份;碳酸氢钠2~8份;含钕配位聚合物7~16份。本发明的固态脱硫剂中通过添加新型的含钕配位聚合物,使得所得的脱硫剂和现有市面常见固态脱硫剂相比具有脱硫效果好,硫容量高的特点。

Description

一种固态脱硫剂
技术领域
本发明涉及脱硫剂,具体涉及一种固态脱硫剂。
背景技术
气化或热解产生的粗煤气中含有粉尘、HCl 和含硫气体 (90%以上为 H2S) 等污染物,在使用之前必须予以净化。煤气作为燃料气使用时,含硫气体会对燃气轮机叶片等设备造成腐蚀;作为原料气则会使催化剂硫中毒,同时其燃烧转化为SO2释放到大气中会引起酸雨,严重危害环境和人体健康,因此在工艺过程中 H2S 等含硫物质的脱除是生活生产中的必要环节。现有的脱硫剂的脱硫率一般较低,脱硫不完全,硫容量低。
发明内容
本发明所要解决的技术问题是提供一种脱硫效果好,硫容量高的固态脱硫剂。
本发明所要解决的技术问题通过以下技术方案予以实现:
一种固态脱硫剂,由如下重量份数的组分组成:
氧化钙3~9份;三氧化二铁5~16份;氟化钙5~10份;氧化铝1~6份;碳酸氢钠2~8份;含钕配位聚合物7~16份。
进一步的,所述含钕配位聚合物的化学式为:C56H48O12N4Nd。
进一步的,所述含钕配位聚合物为单斜晶系,C2/c空间群,晶胞参数为a= 21.573(2) Å,b= 19.739 (9) Å,c= 23.753(3) Å,α=γ=90º,β=101.43(3)º,V=10037.25(5) Å 3
本发明具有如下有益效果:
本发明的固态脱硫剂中通过添加新型的含钕配位聚合物,使得所得的脱硫剂和现有市面常见固态脱硫剂相比具有脱硫效果好,硫容量高的特点。
具体实施方式
下面结合实施例对本发明进行详细的说明,实施例仅是本发明的优选实施方式,不是对本发明的限定。
本发明所用的原料均为市面可得产品。
本发明含钕配位聚合物如无特别说明,均按下述方法制备。
将0.2 mmol4,4'-二甲氧基-[1,1'-联苯基]-3,3'-二羧酸(英文为:4,4'-dimethoxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid,具体结构式如下所示)、0.2mmol4,4'-二甲基-2,2'-联吡啶和0.1 mmol的硝酸钕溶于5 mL水和10 mL二甲基甲酰胺的混合溶剂当中,在室温下搅拌形成混合液A,用无机碱将混合液A的pH调节为8,然后将上述混合液A在60℃下回流12小时得到混合液B。
然后将所述混合液B置入25 mL水热反应釜中在溶剂热160℃条件下加热反应48小时后以5℃/小时降至室温得到所述的含钕配位聚合物。
然后将上述含钕配位聚合物进行结构表征。
该配位聚合物的X射线衍射数据是在Bruker Smart Apex CCD面探衍射仪上,用MoKα辐射(λ = 0.71073 Å),以ω扫描方式收集并进行Lp因子校正,吸收校正使用SADABS程序。用直接法解结构,然后用差值傅立叶法求出全部非氢原子坐标,并用理论加氢法得到氢原子位置(C−H 1.083 Å),用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。
经测试解析可知,该含钕配位聚合物化学分子式为C56H48O12N4Nd,单斜晶系,C2/c空间群,晶胞参数为a= 21.573(2) Å,b= 19.739 (9) Å,c= 23.753(3) Å,α=γ=90º,β=101.43(3)º,V=10037.25(5) Å 3 ,Z=8。
本发明的脱硫剂的制备方法为本技术领域的常用方法,在本发明中不再详细描述。
实施例1
一种固态脱硫剂,由如下重量份数的组分组成:
氧化钙5份;三氧化二铁14份;氟化钙9份;氧化铝2份;碳酸氢钠5份;含钕配位聚合物10份。
实施例2
一种固态脱硫剂,由如下重量份数的组分组成:
氧化钙8份;三氧化二铁6份;氟化钙6份;氧化铝6份;碳酸氢钠8份;含钕配位聚合物15份。
实施例3
一种固态脱硫剂,由如下重量份数的组分组成:
氧化钙3份;三氧化二铁10份;氟化钙7份;氧化铝3份;碳酸氢钠2份;含钕配位聚合物7份。
对比例
一种固态脱硫剂,由如下重量份数的组分组成:
氧化钙5份;三氧化二铁14份;氟化钙9份;氧化铝2份;碳酸氢钠5份。
将上述实施例和对比例所得的固态脱硫剂按照本技术领域的常规性能方法对其检测,性能如表1所示。
表1 固态脱硫剂性能对照表
实施例1 实施例2 实施例3 对比例
脱硫率 87% 92% 83% 68%
硫容量 36% 42% 33% 21%
29 次循环后脱硫率 81% 85% 76% 40%
29次循环后硫容量 25% 28% 22% 7%
从以上数据可知,本发明通过添加新型的含钕配位聚合物,使得所得的脱硫剂具有脱硫效果好,硫容量高的特点。
以上所述实施例仅表达了本发明的实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制,但凡采用等同替换或等效变换的形式所获得的技术方案,均应落在本发明的保护范围之内。

Claims (1)

1.一种固态脱硫剂,其特征在于由如下重量份数的组分组成:
氧化钙3~9份;三氧化二铁5~16份;氟化钙5~10份;氧化铝1~6份;碳酸氢钠2~8份;含钕配位聚合物7~16份;
所述含钕配位聚合物的化学式为:C56H48O12N4Nd;
所述含钕配位聚合物为单斜晶系,C2/c空间群,晶胞参数为a= 21.573(2) Å,b=19.739 (9) Å,c= 23.753(3) Å,α=γ=90 º,β=101.43(3)º,V=10037.25(5) Å 3
所述含钕配位聚合物按照以下方法制备:将0.2 mmol4,4'-二甲氧基-[1,1'-联苯基]-3,3'-二羧酸,0.2 mmol4,4'-二甲基-2,2'-联吡啶和0.1 mmol的硝酸钕溶于5 mL水和10mL二甲基甲酰胺的混合溶剂当中,在室温下搅拌形成混合液A,用无机碱将混合液A的pH调节为8,然后将上述混合液A在60℃下回流12小时得到混合液B;然后将所述混合液B置入25mL水热反应釜中在溶剂热160℃条件下加热反应48小时后以5℃/小时降至室温得到所述的含钕配位聚合物。
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