采用工业焦粉深度处理焦化废水的研究
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摘要
钢铁企业在炼焦、煤气净化及焦化产品回收过程中产生了大量焦化废水。焦化废水是一种浓度高的有机废水,成份复杂、毒性大,若废水中污染物的超标排放,将对环境造成了严重污染,对人类、水产、农作物等都构成了很大危害。而经两次生化处理后的焦化废水,其水质的色度、COD等指标仍难以达到国家排放标准,必须进行进一步的深度处理。针对这一问题,本课题根据焦粉与活性炭理化性质的相似性,提出了利用焦粉代替常规活性炭对经生化处理后的废水进行深度处理的方法。具体做了以下几个方面的研究:
(1)进行焦化生化废水的实验室静态反应研究,考察影响焦粉深度吸附处理焦化废水的各种因素。实验表明:反应的最佳条件是焦粉投加比例为100g焦粉/L废水;平均粒径约为50-60目; pH在2.0~3.0左右;静态吸附时间为3~4h。
(2)进行实验室连续动态小试实验研究,考察连续运行中,焦粉分别对①用稀硫酸调节废水pH至3.0;②在废水中添加0.25‰聚合硫酸铝;③不进行预处理的废水进行吸附处理的效果。实验表明:对废水进行预处理后的吸附效果比不进行预处理的要好,出水的pH值随焦粉逐渐达到吸附饱和而略有减小。
(3)进行废水深度处理扩大试验,考察实际生产中焦粉深度吸附处理焦化废水的运行效果。结果表明:粗焦粉的吸附效果比细焦粉的要好。随着吸附时间的增加,处理后废水的色度不断增加,COD在焦粉吸附达到饱和前,逐渐减小;达到饱和后,开始增大;至焦粉吸附达到饱和时,焦粉对废水中污染物基本不再有吸附作用。
(4)研究吸附饱和后废焦粉掺作烧结料对烧结矿质量的影响情况。结果表明:将吸附饱和后的焦粉用于铁矿石的烧结过程,不会对烧结矿质量产生不利的影响,完全可以替代普通焦粉配用于烧结料中。
(5)进行焦粉深度吸附处理焦化废水的吸附机理研究。动力学实验表明:拟二级动力学方程能很好的描述焦粉吸附深度处理焦化废水的过程,吸附过程除颗粒内扩散外还有液膜扩散的影响;吸附平衡实验表明:该过程为放热反应,Langmuir方程拟合结果最好,能很好的描述该吸附过程。
总的实验结果说明该法用于钢铁冶金企业焦化废水的深度处理具有很好的效果,可同时实现焦化废水达标处理与吸附饱和焦粉内部回用,具有良好工业应用前景。
A large amount of coking wastewater is produced in the coking, coal gas purification and product recovery process by the domestic iron and steel enterprises. The coking wastewater is a kind of complex organic effluent with high concentration and high toxicity. The COD and chroma of coking wastewater couldn’t reach the nation discharge standard with twice biochemical treatment. Aimed at the problems, the issue raised an way of adsorption treatment of the coking wastewater with the extinguishing coke powder instead of active carbon. The specific study is as follows:
(1) Laboratory still experiment: the effect of added coke powder’s quantity, coke powder’s grain diameter, coke wastewater’s pH and adsorption time to treatment effect of the coke wastewater was studied . The results showed that 100g/l of added coke powder’s quantity, 50-60 mesh of coke powder’s grain diameter, pH of the coke wastewater:2.0-3.0 and 3-4h adsorption time were suitable.
(2) Small-scale continuous dynamic experiment: it detected the change of outflow’s pH, chroma and COD with three pretreatments of coking wastewater. The results showed that: with pretreatment of 10%wt sulfuric acid and 0.25‰PFAS, the adsorbed effect of coke powder was almost the same and they are better than the way without any pretreatment.
(3) Enlargement experiment: with rough and fine coke powder as adsorbents, effect of the former is better than the later. Chroma removals continuously added as the time goes by and COD is decreased before coke powder reaching saturation, and increased after that.
(4) Sintering experiment: its results show the adsorption process does not have adverse effects to the process of sintering which means that reusing the coke powder and wastewater can be achieved at the same time.
(5) Kinetics experiment:It is showed by study that the pseudo second orderkinetic model is the best, it is much more suitable for the process; the adsorptionequilibrium showed that the process is an exothermic reaction and the Langmuir equation could properly describe the adsorbed process.
The whole results manifest that dealing with the coking wastewater with coke powder has a good effect. It reaches the aims of reusing of and internal recycling and reusing of coke powder at the same time and has a promising prospect of industrial application.
(1)进行焦化生化废水的实验室静态反应研究,考察影响焦粉深度吸附处理焦化废水的各种因素。实验表明:反应的最佳条件是焦粉投加比例为100g焦粉/L废水;平均粒径约为50-60目; pH在2.0~3.0左右;静态吸附时间为3~4h。
(2)进行实验室连续动态小试实验研究,考察连续运行中,焦粉分别对①用稀硫酸调节废水pH至3.0;②在废水中添加0.25‰聚合硫酸铝;③不进行预处理的废水进行吸附处理的效果。实验表明:对废水进行预处理后的吸附效果比不进行预处理的要好,出水的pH值随焦粉逐渐达到吸附饱和而略有减小。
(3)进行废水深度处理扩大试验,考察实际生产中焦粉深度吸附处理焦化废水的运行效果。结果表明:粗焦粉的吸附效果比细焦粉的要好。随着吸附时间的增加,处理后废水的色度不断增加,COD在焦粉吸附达到饱和前,逐渐减小;达到饱和后,开始增大;至焦粉吸附达到饱和时,焦粉对废水中污染物基本不再有吸附作用。
(4)研究吸附饱和后废焦粉掺作烧结料对烧结矿质量的影响情况。结果表明:将吸附饱和后的焦粉用于铁矿石的烧结过程,不会对烧结矿质量产生不利的影响,完全可以替代普通焦粉配用于烧结料中。
(5)进行焦粉深度吸附处理焦化废水的吸附机理研究。动力学实验表明:拟二级动力学方程能很好的描述焦粉吸附深度处理焦化废水的过程,吸附过程除颗粒内扩散外还有液膜扩散的影响;吸附平衡实验表明:该过程为放热反应,Langmuir方程拟合结果最好,能很好的描述该吸附过程。
总的实验结果说明该法用于钢铁冶金企业焦化废水的深度处理具有很好的效果,可同时实现焦化废水达标处理与吸附饱和焦粉内部回用,具有良好工业应用前景。
A large amount of coking wastewater is produced in the coking, coal gas purification and product recovery process by the domestic iron and steel enterprises. The coking wastewater is a kind of complex organic effluent with high concentration and high toxicity. The COD and chroma of coking wastewater couldn’t reach the nation discharge standard with twice biochemical treatment. Aimed at the problems, the issue raised an way of adsorption treatment of the coking wastewater with the extinguishing coke powder instead of active carbon. The specific study is as follows:
(1) Laboratory still experiment: the effect of added coke powder’s quantity, coke powder’s grain diameter, coke wastewater’s pH and adsorption time to treatment effect of the coke wastewater was studied . The results showed that 100g/l of added coke powder’s quantity, 50-60 mesh of coke powder’s grain diameter, pH of the coke wastewater:2.0-3.0 and 3-4h adsorption time were suitable.
(2) Small-scale continuous dynamic experiment: it detected the change of outflow’s pH, chroma and COD with three pretreatments of coking wastewater. The results showed that: with pretreatment of 10%wt sulfuric acid and 0.25‰PFAS, the adsorbed effect of coke powder was almost the same and they are better than the way without any pretreatment.
(3) Enlargement experiment: with rough and fine coke powder as adsorbents, effect of the former is better than the later. Chroma removals continuously added as the time goes by and COD is decreased before coke powder reaching saturation, and increased after that.
(4) Sintering experiment: its results show the adsorption process does not have adverse effects to the process of sintering which means that reusing the coke powder and wastewater can be achieved at the same time.
(5) Kinetics experiment:It is showed by study that the pseudo second orderkinetic model is the best, it is much more suitable for the process; the adsorptionequilibrium showed that the process is an exothermic reaction and the Langmuir equation could properly describe the adsorbed process.
The whole results manifest that dealing with the coking wastewater with coke powder has a good effect. It reaches the aims of reusing of and internal recycling and reusing of coke powder at the same time and has a promising prospect of industrial application.
引文
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[2]中华人民共和国国务院.国民经济和社会发展第十一个五年规划纲要.北京:新华社,2006.
[3]中华人民共和国国务院.国家中长期科学和技术发展规划纲要.北京:国家中长期科学和技术发展规划纲要,2006.
[4]胡任贤,郭亚兵.焦化废水及其处理技术[J].机械工程与自动化, 2004, 126 (5): 97-100.
[5]魏新利,李洁.焦化废水处理技术的应用与研究进展[J].环境污染与防治,2004,1:25-26.
[6]孔令东,姜成春.焦化废水的处理及废水中有机污染物的测定[J].环境工程,1994,12(4):3-6.
[7]连军.焦化废水的多污染物评价[J].环境科学动态,2004,2:30-31.
[8]钱易,张辉明.焦化废水中难降解有机物去除的研究[J].环境科学研究,1992,5(5):1-9.
[9]王绍文,钱雷.焦化废水无害化处理与回用技术[M].北京:冶金工业出版社,2005:1-4.
[10]张锦,李圭白等.含酚废水的危害及处理方法的特点[J].化学工程师,2001,11(2):36-37.
[11]叶建锋.废水生物脱氮处理新技术[M].北京:化学工业出版社,2006:85-90.
[12]蔡昌卫.焦化废水的预处理[J].冶金丛刊,2002,137(3):44-45.
[13]吕鉴,贾燕兵.焦化废水预处理[J].工业用水与废水,2000,31(3):23-24.
[14]史晓燕,肖波,杨家宽.焦化废水脱氮处理技术进展[J].环境技术,2003,6:44-48.
[15]张文成,安立超.焦化废水脱氨处理技术进展,环境污染治理技术与设备[J].2004,5(3):23-27.
[16]余蜀宜.用松香胺萃取处理含酚废水的研究[J].化工环保.1999,19(2):80-83.
[17]赵玲,吴梅.混凝澄清在焦化废水处理中的应用.冶金动力,2003,97(3):61-62.
[18]刘梅英等.新型混凝剂聚合氯化铝钙的合成及其初步应用[J].东北大学学报,2005,5(5): 500-503.
[19]杜鸿章,房廉清等.难降解高浓度有机废水催化湿式氧化净化技术[J].水处理技术,1997,23(3):160-63.
[20]Jogle H S Kar,Samant S D,Joshi J E.Kinetics of Wet Air Oxidation of Phenol and Substituted Phenols[J].Wat Res,1991,25(2):135-145.
[21]Oshima Y,Inaba K,Koda S.Catalytic supeicritical water oxidation of coke woks waste with manganese oxide [J].Sekiyu Gakkaishi ,2001,44(6):343-350.
[22]邢素青,王增长.焦化废水处理技术的研究进展[J].科技情报开发与经济,2005,15(23):141-142.
[23]刘红,周志辉,吴克明.Fenton试剂催化氧化-混凝法处理焦化废水的实验研究[J].环境科学与技术,2004,(2):79-81.
[24]卢建航,王红斌.焦化废水专用混凝剂对污染物的去除效果与规律[J].环境科学,2001,2 (7):65-68.
[25]刘翠华,何选明.絮凝剂在焦化废水再净化中的应用[J].武汉冶金科技大学报,1999,22(1) :42-45.
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