高硫废渣催化热解高效脱硫工艺及机理研究  

Mechanism of Efficient Desulfurization Process by Catalytic Pyrolysis for High Sulfur Waste Residue

作　　者：陈浩 王振坤 朱军强 周林 李伟奇 王忠兵 胡文静 玉增蒙 周朝锋 CHEN Hao;WANG Zhenkun;ZHU Junqiang;ZHOU Lin;LI Weiqi;WANG Zhongbing;HU Wenjing;YU Zengmeng;ZHOU Chaofeng(Jiangxi Dongjiang Environmental Protection Technology Co Ltd,Fengcheng 331100,Jiangxi,China;The Second Xiangya Hospital of Central South University,Changsha 410012,Hunan,China;Dongjiang Environmental Co Ltd,Shenzhen 518057,Guangdong,China;Guangdong Provincial Key Laboratory of Hazardous Liquid Waste Reclamation and Advanced Treatment Technology Research and Development Enterprise,Shenzhen 518057,Guangdong,China)

机构地区：[1]江西东江环保技术有限公司,江西丰城331100 [2]中南大学湘雅二医院,湖南长沙410012 [3]东江环保股份有限公司,广东深圳518057 [4]广东省危险废液资源化与深度处理技术研发企业重点实验室,广东深圳518057

出　　处：《矿冶工程》2024年第2期112-118,共7页Mining and Metallurgical Engineering

基　　金：广东省科技计划项目(2018B030323016)。

摘　　要：对高硫废渣开展了催化热解脱硫研究。结果表明,以Fe_(2)O_(3)为固硫剂,在热解温度600℃、热解时间90 min、固硫剂与废渣质量比1.5∶1条件下,总硫去除率为85%左右;废渣中易挥发性含硫复杂有机物转化成稳定的无机物,其中无定形硫可转化为纯度大于95%的晶型硫;废渣热解脱硫后尾渣中残留物主要成分为硫酸钠、炭黑等无机盐;外排废气中主要成分为CH_(4)、C_(2)H_(4)等简单分子有机物,以及少量的CO、SO_(2)、CO_(2)、HCl等无机化合物。热解脱硫过程主要分为4个阶段:(1)非晶单质硫首先发生气化,并发生晶化反应;(2)被有机物附着具有相对更稳定结构的单质硫与有机相的羟基或羧基键发生断裂,硫向外扩散溢出至大气中;(3)含硫有机相在亚甲基、次甲基位发生脱基团反应,生成HCl、H_(2)S和炭黑,并被固硫剂吸附转化为硫酸盐;(4)脱基团后造成氮杂环烃之间碳碳键不稳定,断裂成CH_(4)、C_(2)H_(4)等小分子有机物,以及炭黑和少量H_(2),C—N/C—NH_x键断裂成NO_(x)/NH_(3),C—S/C—SO_(3)H键断裂成H_(2)S、SO_(2),被固硫剂吸附并转化为硫酸盐。Based on the studies of catalytic pyrolysis for high⁃sulfur waste residue(HSWR),it is found that after 90 min pyrolysis at a temperature of 600℃,with Fe_(2)O_(3) as a sulfur fixation agent in a mass ratio of 1.5∶1 with HSWR,the total desulfurization rate can be around 85%.The volatile sulfur⁃containing complex organic matter in HSWR could be transformed into stable inorganic matter,among which the amorphous sulfur could be transformed into crystalline sulfur with purity over 95%.In the residue left after pyrolysis process for desulfurization,the main components include inorganic salts such as sodium sulfate and carbon black.The exhaust gas is mainly composed of simple molecular organics such as CH_(4) and C_(2)H_(4),and a small amount of inorganic compounds such as CO,SO_(2),CO_(2) and HCl.The pyrolysis process for desulfurization consists of four stages:firstly,the amorphous elemental sulfur is vaporized and then crystallized to form crystal sulfur;secondly,as for the elemental sulfur with attachment of organic matter and in a relatively more stable structure,its bond with the hydroxyl or carboxyl of organic phase is broken,leading to sulfur emitted into the atmosphere;at the third stage,the sulfur⁃containing organic phase is deactivated at the methylene and submethyl sites to form HCl,H_(2)S and carbon black,which are then adsorbed by sulfur⁃fixation agent and converted into sulfate;at the fourth stage,the carbon⁃carbon bond between nitrogen heterocyclic hydrocarbons becomes unstable after grouping,and is broken into small organic molecules such as CH_(4) and C_(2)H_(4),as well as carbon black and a trace of H_(2).Meanwhile,C—N/C—NHx bonds are broken into NO_(x)/NH_(3),and C—S/C—SO_(3)H bonds are broken into H_(2)S and SO_(2),which are then adsorbed by sulfur fixation agents and converted into sulfate.

关 键 词：高硫废渣 催化热解 脱硫 固硫剂 无害化 有机硫 硫酸盐 

分 类 号：X788[环境科学与工程—环境工程]