酸洗废液及污泥制备磁性氧化铁颜料的工艺
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摘要
以金属制品厂酸洗废液与酸洗污泥为原材料,采用湿式沉淀法制备高性能磁性氧化铁(Fe3O4)颜料。实验采用双氧水为氧化剂,15%石灰浆液调节反应液pH,利用蒸汽加热法为体系升温,以终点Fe~(3+)/Fe~(2+)比为判断依据,分析了废酸/污泥比、原液Fe~(3+)/Fe~(2+)比、反应时间、pH、反应温度对合成Fe3O4产品的影响。结果表明,随着实验不断进行,受空气影响,反应过程中Fe~(3+)/Fe~(2+)比是逐渐升高的;在废酸/污泥比为5∶1、原液Fe~(3+)/Fe~(2+)比为1.60∶1、反应时间为4h、p H为9、反应温度介于80～90℃之间条件下,合成产物色光及吸油量等指标达到氧化铁黑标准要求。本研究解决了行业内酸洗污泥资源化处置的瓶颈问题,为企业带来经济效益及环境效益。
The preparation of high-performance magnetic iron oxide(Fe3O4) pigment from pickling waste liquid and acid-washed sludge was explored by wet precipitation method. In the experiment, hydrogen peroxide was used as oxidant, 15% lime slurry was used to regulate the p H of reaction liquid, steamheating method was used as heating system. Based on the ratio of end-point Fe~(3+)/Fe~(2+), the influence ofsludge volume, Fe~(3+)/Fe~(2+) ratio, reaction time, pH and reaction temperature on the synthesis of Fe3O4 wereanalyzed. The results showed that the ratio of Fe~(3+)/Fe~(2+)increased gradually under the influence of airduring the reaction. Magnetic iron oxide pigment with high quality was obtained under the conditions ofpickling wastewater/sludge ratio 5∶ 1, Fe~(3+)/Fe~(2+) ratio 1.60∶ 1, reaction time 4h, p H 9 and reaction temperature 80-90℃.The color light and oil absorption of the product can reach the black iron oxide standard.This study could solve the bottleneck problem of the resource treatment of acid-washed sludge in the industry and bring economic and environmental benefits to enterprises.
The preparation of high-performance magnetic iron oxide(Fe3O4) pigment from pickling waste liquid and acid-washed sludge was explored by wet precipitation method. In the experiment, hydrogen peroxide was used as oxidant, 15% lime slurry was used to regulate the p H of reaction liquid, steamheating method was used as heating system. Based on the ratio of end-point Fe~(3+)/Fe~(2+), the influence ofsludge volume, Fe~(3+)/Fe~(2+) ratio, reaction time, pH and reaction temperature on the synthesis of Fe3O4 wereanalyzed. The results showed that the ratio of Fe~(3+)/Fe~(2+)increased gradually under the influence of airduring the reaction. Magnetic iron oxide pigment with high quality was obtained under the conditions ofpickling wastewater/sludge ratio 5∶ 1, Fe~(3+)/Fe~(2+) ratio 1.60∶ 1, reaction time 4h, p H 9 and reaction temperature 80-90℃.The color light and oil absorption of the product can reach the black iron oxide standard.This study could solve the bottleneck problem of the resource treatment of acid-washed sludge in the industry and bring economic and environmental benefits to enterprises.
引文
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[13]李雁,徐明仙,林春绵.硫铁矿废水制备铁黑颜料的工艺[J].化工进展, 2010, 29(1):168-172.LI Yan, XU Mingxian, LIN Chunmian. Preparation of black ironpigment from iron pyrite wastewater[J]. Chemical Industry andEngineering Progress, 2010, 29(1):168-172.
[14]周宏明.钛白副产硫酸亚铁制备氧化铁系颜料工艺的研究[D].湘潭:湘潭大学, 2001.ZHOU Hongming.Study on the craft of preparing iron oxide pigmentfrom by-product of TiO2—ferrous sulfate[D]. Xiangtan:XiangtanUniversity, 2001.
[15]沈腊珍.利用钢厂除尘灰合成纳米级磁性氧化铁黑颜料的研究[D].天津:天津大学, 2004.SHEN Lazhen. Synthesis of nanometer-sized magnetic black Ironoxide pigment by using dust of steel industry[D]. Tianjin:TianjinUniversity, 2004.
[2]房金乐,杨文涛.不锈钢酸洗污泥的处理现状及展望[J].中国资源综合利用, 2014, 32(11):24-27.FANG Jinle, YANG Wentao. Present situation and prospect oftreatment of stainless steel pickling[J]. China ResourcesComprehensive Utilization, 2014, 32(11):24-27.
[3]揭超,解付兵,毛建军,等.钢材酸洗废液制取高纯Fe2O3工艺研究[J].矿冶工程, 2003, 23(2):49-52.JIE Chao, XIE Fubing, MAO Jianjun, et al.Technology for preparinghigh-purity Fe2O3from steel-washing waste acid[J]. Mining andMetallurgical Engineering, 2003, 23(2):49-52.
[4]高亮.不锈钢酸洗废水处理中的污泥减排技术[J].中国给水排水,2009, 25(10):83-86.GAO Liang. Sludge reduction technology in stainless steel acidcleaning wastewater treatment[J].China Water&Wastewater, 2009,25(10):83-86.
[5]周光升,俞国安.冷轧不锈钢酸洗废酸焙烧法回收工艺评述[J].宝钢技术, 2003(s1):1-2.ZHOU Guangsheng, YU Guoan. Review on the recovery process ofroasting stainless steel pickling waste acid[J]. Baosteel Technology,2003(s1):1-2.
[6] MURASE T, HIRAI N. Recent evelopment of iron oxide for ferriteand its manufacturing technique from pickling waste liquor of steelsheet[J].Tetsu-to-Hagane, 2009, 79(10):1129-1137.
[7]付伟,邵晓周.外循环减压蒸发工艺回收废酸技术与应用[J].环境污染与防治, 2004, 26(3):227-228.FU Wei, SHAO Xiaozhou.Technology and application of recovery ofwaste acid by external loop vacuum evaporation process[J].Environmental Pollution and Prevention, 2004, 26(3):227-228.
[8] NEGRO C, BLANCO M A, LOPEZ-MATCOS F, et al.Free acids andchemicals recovery from stainless steel pickling baths[J].SeparationScience and Technology, 2001, 6(7):1543-1556.
[9] KUPPINGER F F. Method for the production of hydrochloric acidswith concentration above the concentration of the water/HCl azeotrope:DE19850398[P].2000-05-04.
[10]李潜,朱红力.萃取法回收钛白水解废酸中的硫酸[J].化工环保.2003, 23(4):225-228.LI Qian, ZHU Hongli. Recovery of sulfuric acid from titaniumhydrolysis waste acid by extraction[J]. Environmental Protection ofChemical Industry,2003, 23(4):225-228.
[11]周连江,乐志强,吕秉玲,等.无机盐工业手册[M].2版.北京:化学工业出版社, 1996:963-978.ZHOU Lianjiang, YUE Zhiqiang, LüBingling, et al. Inorganic saltindustry manual[M]. 2nd ed. Beijing:Chemical Industry Press,1996:963-978.
[12]朱骥良,吴申年.颜料工艺学[M].北京:化学工业出版社, 1989:2-4.ZHU Jiliang, WU Shennian.The technique of pigments[M].Beijing:Chemical Industry Press, 1989:2-4.
[13]李雁,徐明仙,林春绵.硫铁矿废水制备铁黑颜料的工艺[J].化工进展, 2010, 29(1):168-172.LI Yan, XU Mingxian, LIN Chunmian. Preparation of black ironpigment from iron pyrite wastewater[J]. Chemical Industry andEngineering Progress, 2010, 29(1):168-172.
[14]周宏明.钛白副产硫酸亚铁制备氧化铁系颜料工艺的研究[D].湘潭:湘潭大学, 2001.ZHOU Hongming.Study on the craft of preparing iron oxide pigmentfrom by-product of TiO2—ferrous sulfate[D]. Xiangtan:XiangtanUniversity, 2001.
[15]沈腊珍.利用钢厂除尘灰合成纳米级磁性氧化铁黑颜料的研究[D].天津:天津大学, 2004.SHEN Lazhen. Synthesis of nanometer-sized magnetic black Ironoxide pigment by using dust of steel industry[D]. Tianjin:TianjinUniversity, 2004.