基于微波辅助脱除硫醇甲基锡废底料中的氯

doi:10.16085/j.issn.1000-6613.2018-2421

摘要/Abstract

摘要：

以硫醇甲基锡废底料为研究对象，通过元素组成和XRD分析，结合废底料物性特征，设计了微波辅助干馏回收低沸点物质，残渣脱氯后用作锡冶炼精料的基本构思。实验研究表明：干馏可回收质量分数约15.86%的低沸点物质，同时可脱除约31.06%的氯。以残渣中氯含量为考察指标，系统研究了残渣与过氧化氢液固比、氧化静置时间、残渣与浓硫酸液固比、微波强化时间对氯脱除率的影响，结果表明：过氧化氢与残渣液固比为1∶5、氧化静置时间为30min、浓硫酸与残渣液固比为1∶3、微波强化时间为80min时，残渣中氯质量分数为0.59%，氯的脱除率可达到97.48%，满足企业锡冶炼精料氯质量分数＜0.8%要求。通过对微波浸取机制讨论以及残渣XRD、SEM的表征，初步对干馏残渣脱氯过程进行了机理分析，为硫醇甲基锡废底料中氯的脱除提供了理论依据，研究成果具有较好的应用前景。

关键词: 硫醇甲基锡废底料, 微波辅助, 干馏, 脱氯

Abstract:

The mercaptan methyl tin waste stock was used as research object. Based on the element composition, XRD analysis and the feature of physical properties of the waste base, the study designed a basic idea that microwave-assisted dry distillation recovery of low-boiling substances from the waste stock was adopted and dechlorinated residue was taken as the tin smelting concentrate. The experimental results showed that dry distillation can recycle about 15.86% of low boiling matter and remove about 31.06% of chlorine. We systematically studied the effect of liquid-solid ratio of residue to hydrogen peroxide, oxidation standing time of hydrogen peroxide,liquid-solid ratio of residue to concentrated sulfuric acid and microwave hardening time on the removal ratios of chlorine. With liquid-solid ratio of hydrogen peroxide being 1∶5, oxidation standing time of hydrogen peroxide being 30min, liquid-solid ratio of residue to concentrated sulfuric being 1∶3 and microwave hardening time being 80min, the chlorine content in the residue was 0.59% and the chlorine removal rate could reach 97.48%, which meet the requirements of the enterprise tin smelting concentrate chlorine content less than 0.8%. Meanwhile, the mechanism of microwave leaching and characterization of residue by XRD and SEM were discussed, after which the dechlorination process of dry distillation residue was analyzed. This provided the theoretical basis for industrial removal of chlorine from mercaptan methyl tin waste stock. In addition, the research results had better application prospect.

Key words: mercaptan methyl tin waste stock, microwave assisted, dry distillation, dechlorination

中图分类号:

X756

郑光亚, 夏举佩, 李银, 陈正杰, 刘成龙. 基于微波辅助脱除硫醇甲基锡废底料中的氯[J]. 化工进展, 2019, 38(07): 3443-3449.

Guangya ZHENG, Jupei XIA, Yin LI, Zhengjie CHEN, Chenglong LIU. Microwave-assisted removal of chlorine from mercaptan methyl tin waste stock[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3443-3449.

图/表 12

表1 原料主要化学元素组成

组成元素	质量分数/%
Sn	58.36
Cl	28.78
S	6.32
O	3.02
C	1.21
H	0.75
N	0.68

图1 实验干馏装置图

图2 原料XRD衍射图谱

图3 干馏产品XRD衍射图谱

图4 干馏残渣XRD衍射图谱

图5 过氧化氢与残渣液固比对脱氯的影响

图6 过氧化氢氧化静置时间对脱氯的影响

图7 浓硫酸与残渣液固比对脱氯的影响

图8 微波强化时间对脱氯的影响

图9 脱氯残渣XRD衍射图谱

图10 干馏残渣SEM图像

图11 脱氯残渣SEM图像

参考文献 23

1	李祥彦, 易强顺, 朱朝刚. 硫醇甲基锡在PVC加工中的热稳定性及加工性能测试[J]. 云南化工, 2015, 42(1): 18-20.
	LIXiangyan, YIQiangshun, ZHUChaogang. Thermal stability and processing performance testing of methyl mercaptan in PVC[J]. Yunnan Chemical Technology, 2015, 42(1): 18-20.
2	王爱红, 韩永和, 李尖, 等. 硫醇甲基锡合成方法研究[J]. 塑料助剂, 2013(4): 24-26.
	WANGAihong, HANYonghe, LIJian, et al. Study on the synthesis methods of methylitin mercaptide[J]. Plastics Additives, 2013(4): 24-26.
3	沅文响. 甲基硫醇锡的生产合成工艺[J]. 塑料助剂, 2001(5): 11-12.
	YUANWenxiang. Production and synthesis process of methyl mercaptan tin[J]. Plastics Additives, 2001(5):11-12.
4	王伟, 景箫, 秦光和. 硫醇甲基锡化合物急性经口毒性试验结果分析[J]. 中国卫生检验杂志, 2006(11): 1375-1376.
	WANGWei, JINGXiao, QINGuanghe. Analysis of acute oral toxicity test results of thiol methyl tin compounds[J]. Chinese Journal of Health Laboratory Technology, 2006(11): 1375-1376.
5	玄立春. 危险固体废弃物环境影响评价[J]. 中国科技投资, 2018(5): 335-337.
	XUANLichun. Environmental impact assessment of hazardous solid waste[J]. China Venture Capital, 2018(5): 335-337.
6	潘旭东, 王向明. 循环水中氯离子控制及对不锈钢腐蚀机理探讨[J]. 工业水处理, 2013, 33(3): 14-16.
	PANXudong, WANGXiangming. Control of chloride ions in circulating water and influence on stainless steel corrosion[J]. Industrial Water Treatment, 2013, 33(3):14-16.
7	赵春梅, 王正君. 氯离子的腐蚀机理分析及防腐处理[J]. 黑龙江水利科技杂志, 2016, 2(7): 6-9.
	ZHAOChunmei, WANGZhengju. Research progress in the mechanism of chloride ion corrosion and anticorrosion[J]. Heilongjiang Science and Technology of Water Conservancy, 2016, 2(7): 6-9.
8	HUPing, SONGRui, LIXiaojing, et al. A influence of concentrations of chloride ions on electrochemical corrosion behavior of titanium-zirconium-molybdenum alloy[J]. Journal of Alloys and Compounds, 2017, 708: 367-372.
9	RODRIGUESA V, OLIVEIRAN T C, SANTOS M LDOS, et al. Electrochemical behavior and corrosion resistance of Ti-15Mo alloy in naturally-aerated solutions, containing chloride and fluoride ions[J]. Journal of Materials Science, 2015, 26(1): 259-263.
10	李瑞丽, 李晶晶, 张平. 吸附法脱除模拟油中有机氯[J]. 化工进展, 2017, 36(4): 1470-1475.
	LIRuili, LIJingjing, ZHANGPing. Removal of organic chlorine in simulated oil by adsorption[J]. Chemical Industry and Engineering Progress, 2017, 36(4): 1470-1475.
11	孙红燕, 森维, 孔馨, 等. 离子交换法从锌电解液中脱除氯试验研究[J]. 湿法冶金, 2017, 36(2): 133-136.
	SUNHongyan, WeiSEN, KONGXin, et al. Removal of chlorine from zinc electrolyte by ion exchange[J]. Hydrometallurgy of China, 2017, 36(2): 133-136.
12	张月萍, 赵平, 李彦坤. 古龙酸发酵废液氯离子脱除的研究[J]. 现代化工, 2014, 34(2): 93-96.
	ZHANGYueping, ZHAOPing, LIYankun. Dechlorination of gulonic acid fermentation waste[J]. Modern Chemical Industry, 2014, 34(2): 93-96.
13	彭金辉, 黄孟阳, 张正勇, 等. 微波加热浸出初级富钛料非等温动力学及吸波特性[J]. 中国有色金属学报, 2008, 18(s1): 207-214.
	PENGJinhui, HUANGMengyang, ZHANGZhengyong, et al. Non-isothermal kinetics and absorption property of leaching primary titanium-rich materials by microwave heating[J]. The Chinese Journal of Nonferrous Metals, 2008, 18(s1): 207-214.
14	冯建华, 兰新哲, 宋永辉, 等. 微波辅助技术在湿法冶金中的应用[J]. 湿法冶金, 2008, 27(4): 211-215.
	FENGJianhua, LANXinzhe, SONGYonghui, et al. Application of microwave-assisted technique in hydrometallurgy[J]. Hydrometallurgy of China, 2008, 27(4): 211-215.
15	万勇, 于少明, 陆亚玲, 等. 蛇纹石微波辐照硫酸浸出的实验研究[J]. 矿物学报, 2004, 24(4): 347-350.
	WANYong，YUShaoming，LUYaling，et al. Experimental study on sulfuric acid leaching of serpentine by microwave irradiation[J]. Acta Mineralogica Sinica, 2004, 24(4): 347-350.
16	丁伟安. 微波辐射作用下硫化钢精矿三氯化铁浸出[J]. 湿法冶金, 1996, 15(1): 53-55.
	DINGWeian. Sulfide steel concentrate leaching of ferric chloride under microwave irradiation[J]. Hydrometallurgy of China, 1996, 15(1): 53-55.
17	司士辉, 戚斌斌. 微波场对石煤湿法提钒过程的影响[J]. 常熟理工学院学报, 2009, 23(2): 50-54.
	SIShihui, QIBinbin. The microwave infection on the extraction of vanadium from stone coal[J]. Journal of Changshu Institute of Technology, 2009, 23(2): 50-54.
18	程一澈. 论高中化学中双氧水和过氧化氢的常见问题[J]. 同行, 2016 (15): 437.
	CHENGYiche. Common problems of hydrogen peroxide and hydrogen peroxide in high school chemistry[J]. Travel Together, 2016(15): 437.
19	王水连, 辛贤. 农户甘蔗种植机械化的因素解析:诱因及交互效应[J]. 中国农业大学学报, 2017, 34(1): 83-93.
	WANGShuilian, XINXian. Analysis of sugarcane planting mechanization factors and its interactive effects[J]. Journal of China Agricultural University, 2017, 34(1): 83-93.
20	康娟, 周雯, 权维强, 等. 微波强化零价铁-芬顿法降解罗丹明 B的研究[J]. 环境科学与技术, 2015, 38 (12): 205-209.
	KANGJuan, ZHOUWen, QUANWeiqiang, et al. Degradation of Rhodamine B by microwave enhanced zero valent iron-fenton process[J]. Environmental Science & Technology, 2015, 38 (12): 205-209.
21	严宝珍. 甲基氯化锡的核磁共振波谱研究[J]. 分析测试学报,1990, 9(1): 64-67.
	YANBaozhen. Nuclear magnetic resonance spectroscopy study of methyltin chloride[J]. Journal of Instrumental Analysis, 1990, 9(1): 64-67.
22	代佼, 李林, 王正虹, 等. 气相色谱法测定食品塑料包装材料中三甲基氯化锡[J]. 理化检验(化学分册), 2012, 48(8): 900-902.
	DAIJiao, LILin, WANGZhenghong, et al. GC determination of trimethyl tin chloride in plastic food packaging material[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis), 2012, 48(8): 900-902.
23	陈德友. 活化分子有效碰撞问题的探析[J]. 中学化学, 2013(6): 17-18.
	CHENDeyou. Analysis on the effective collision of activated molecules[J]. Middle School Chemistry, 2013(6): 17-18.

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