沉淀-氧化法处理乙烯废碱液
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摘要
采用沉淀-氧化法处理乙烯废碱液中的硫化物,考察了影响脱硫效果的各种因素。在n(CuSO4)∶n(Na2S)=1.1∶1、温度为40℃、时间为0.5h条件下,沉淀法脱硫后碱液残留的S2-浓度为0.04g/L;然后进一步采用双氧水氧化处理脱硫后碱液,在氧化反应温度为40℃、时间为2h、氧化剂双氧水用量为1.0mL/L废碱液时,乙烯废碱液中的S2-浓度可降至1mg/L以下,达到湿式氧化的处理效果和烟气脱硫对乙烯废碱液的要求。同时硫酸铜湿法氧化再生研究结果表明:在硫化铜浆液质量分数为15%、pH=3、氧分压为0.5MPa、温度为200℃、时间为0.5h的条件下,硫酸铜再生彻底,实现了硫酸铜的循环利用。
Precipitation-oxidation process was used to treat sulfide in ethylene waste lye. The factors affecting removing efficiency were investigated. Under the condition of n(CuSO4)∶ n(Na2 S)=1.1∶ 1、temperature 40℃ and 2 h, S2-in lye residue after desulfurization by precipitation was 0.04 g/L. Then the lye after desulphurization was further treated by oxidation with hydrogen peroxide. When the oxidation reaction temperature is 40℃, the time is 2 h, and the amount of oxidant hydrogen peroxide is 1.0 mL/L waste lye, The S2-in ethylene waste lye could be reduced to below 1 mg/L, and it meets the treatment effect of wet oxidation technology and the requirements of flue gas desulfurization for ethylene waste lye. At the same time, wet oxidation regeneration of copper sulfate was also studied. The results showed that: under the conditions of 15% concentration of copper sulfide slurry, pH=3, oxygen partial pressure of 0.5 MPa,reaction temperature of 200℃, and reaction time of 0.5 h, copper sulfate regeneration was complete. The recycling utilization of copper sulfate was realized.
Precipitation-oxidation process was used to treat sulfide in ethylene waste lye. The factors affecting removing efficiency were investigated. Under the condition of n(CuSO4)∶ n(Na2 S)=1.1∶ 1、temperature 40℃ and 2 h, S2-in lye residue after desulfurization by precipitation was 0.04 g/L. Then the lye after desulphurization was further treated by oxidation with hydrogen peroxide. When the oxidation reaction temperature is 40℃, the time is 2 h, and the amount of oxidant hydrogen peroxide is 1.0 mL/L waste lye, The S2-in ethylene waste lye could be reduced to below 1 mg/L, and it meets the treatment effect of wet oxidation technology and the requirements of flue gas desulfurization for ethylene waste lye. At the same time, wet oxidation regeneration of copper sulfate was also studied. The results showed that: under the conditions of 15% concentration of copper sulfide slurry, pH=3, oxygen partial pressure of 0.5 MPa,reaction temperature of 200℃, and reaction time of 0.5 h, copper sulfate regeneration was complete. The recycling utilization of copper sulfate was realized.
引文
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[18]许志忠,李晓春.过氧化氢分解影响因素分析[J].染整技术, 2006,28(1):34-35, 38.XU Z Z, LI C X. Analysis of influencing factors on hydrogen peroxide decomposition[J]. Textile Dyelng and Finshing Journal, 2006, 28(1):34-35, 38.
[2]邵李华,韩建华,邓德刚.湿式氧化工艺处理乙烯废碱液的开工运行[J].石油化工环境保护, 2004, 27(2):56-58.SHAO L H, HAN J H, DENG D G. Wet air oxidation process for spent caustic treatment-startup scheme and operating[J]. Environmental Protection in Petrochemical Industry, 2004, 27(2):56-58.
[3]蓝春树. EM-BAF技术在乙烯废碱液处理中的应用[J].化工进展,2009, 28(s2):199-202.LAN C S. Application of EM-BAF technology in the treatment of ethylene lye[J]. Chemical Industry and Engineering Progress, 2009, 28(s2):199-202.
[4]产文兵,万皓,宋桂东,等.纳碱法烟气脱硫工艺技术[J].上海大学学报, 2013(5):474-478.CHAN W B, WAN H, SONG G D, et al. FGD process technology with sodium alkaline method[J]. Journal of Shanghai University, 2013(5):474-478.
[5]牟义慧,洪运武,刘振兴.废碱法烟气脱硫吸收塔和烟囱的腐蚀与防护[J].石油化工腐蚀与防护, 2015, 32(4):59-61.MU Y H, HONG Y W, LIU Z X. Corrosion of absorption tower and stack of spent caustic flue gas desulphurization and protection[J].Corrosion&Protection in Petrochemical Industry, 2015, 32(4):59-61.
[6]范向东,顾晓婧,何仁初,等.几种消泡剂在乙烯废碱液脱硫过程中的消泡性能研究[J].化学工程与技术, 2015(5):13-20.FAN X D, GU X J, HE R C, et al. Study on the defoaming performance of several defoaming agents in the desulfurization process using ethylene waste alkali liquor[J]. Journal of Chemical Engineering and Technology, 2015(5):13-20.
[7]张秀红,童键,孙德智.化学沉淀法处理乙烯裂解废碱液中的硫化物[J].化学工程师, 2004(8):41-44.ZHANG X H, TONG J, SUN D G. The treatment of sulfide in spent caustic from ethylene precipitation[J]. Chemical Engineer, 2004(8):41-44.
[8]余政哲,孙德智,史鹏飞,等.化学沉淀与高级氧化法处理乙烯裂解废碱液的研究[J].化工环保, 2004, 24(2):90-94.YU Z Z, SUN D Z, SHI P F, et al. Study on the treatment of waste alkali in ethylene cracking by chemical precipitation-advanced oxidation peocess[J]. Environment Protection of Chemical Industry,2004, 24(2):90-94.
[9]河北工业大学.一种乙烯碱洗废液再生处理工艺:CN200510122185[P]. 2006-06-21.Hebei University of Technology. A reprocessing technology for ethylene alkaline wash waste liquid:CN200510122185[P]. 2006-06-21.
[10]中国石油天然气股份有限公司.一种酸性气碱洗废液的处理方法:CN102815815B[P]. 2011-06-10.PetroChina Co., Ltd. A treatment method of acid-alkali washing waste liquid:CN102815815B[P]. 2011-06-10.
[11]吴林美,杜龙弟,李向富,等.乙烯废碱液再生回用的可行性研究[J].现代化工, 2006, 26(s2):350-352.WU L M, DU L D, LI X F, et al. Feasibility study on regeneration and reuse of spent caustic from ethylene plant[J]. Modern Chemical Industry, 2006, 26(s2):350-352.
[12]刘大星.湿法炼铜的发展与前景[J].有色金属再生与利用, 2005(7):34-36.LIU D X. The development and prospect of wet copper smelting[J].Non-ferrous Metals Recycling and Utilization, 2005(7):34-36.
[13]徐志峰,李强,王成彦.复杂硫化铜精矿微波活化预处理加压浸出工艺[J].过程工程学报, 2010, 10(2):256-262.XU Z F, LI Q, WANG C Y. Microwave activation pretreatment and pressure leaching of complex copper sulfide concentrate[J]. Chinese Journal of Process Engineering, 2010, 10(2):256-262.
[14] F·哈伯锡.加压湿法冶金[J].国外金属矿选矿, 2006(11):10-15.HABOSEY F. Pressurized hydrometallurgy[J]. Metallic Ore Dressing Abroad, 2006(11):10-15.
[15]《水和废水监测分析方法》编委会.水和废水监测分析方法[M]. 4版.北京:中国环境科学出版社, 2002:133-139.The Editorial Board of Standard Methods for the Examination of Water and Waste Water. Standard methods for the examination of water and waste water[M]. 4th ed. Beijing:China Environmental Science Press,2002:133-139.
[16]韩建华.湿式空气氧化法处理石化废碱液[C]//李大东,等.中国石油学会第五届石油炼制学术年会.北京:中国石化出版社, 2006:822-833.HAN J H. Treatment of petrochemical waste soda by wet air oxidation[C]//LI D D,et al. The 5th Annual Petroleum Refining Conference of the China Petroleum Society. Beijing:China Petrochemical Press,2006:822-833.
[17]陈咏梅,陈聪,杨晓进,等.控制硫酸铜加入量实现脱硫废水回用的初步研究[J].工业水处理, 2012, 32(2):70-72.CHEN Y M, CHEN C, YANG X J, et al. Pilot study on the recycling of desulfurization wastewater by controlling the addition amount of copper sulfate[J]. Industrial Water Treatment, 2012, 32(2):70-72.
[18]许志忠,李晓春.过氧化氢分解影响因素分析[J].染整技术, 2006,28(1):34-35, 38.XU Z Z, LI C X. Analysis of influencing factors on hydrogen peroxide decomposition[J]. Textile Dyelng and Finshing Journal, 2006, 28(1):34-35, 38.