焦化废水深度处理及回用技术方案探讨

对我国当前焦化废水深度处理技术的研究应用情况以及回用现状进行了介绍,分析了焦化废水回用中存在的问题,并提出了改进方案。     

基于机器学习和情景分析的我国焦化行业企业用地污染预测

针对焦化行业企业用地缺乏时序连续监测数据而无法预测其污染趋势的问题,从企业特征、企业管理水平、污染物特征和自然地理要素等4个方面选取13个影响企业用地污染的指标,识别焦化行业企业用地污染主控因子,在此基础上构建基于机器学习的焦化行业企业用地污染预测模型,并在不同情境下,对2025年和2030年焦化行业企业用地污染状况进行预测.结果表明,生产经营活动时间、建厂时间、企业环境监管记录、土壤黏粒和年均风速是焦化行业企业用地污染的主控因子;相对于支持向量机模型、BP神经网络模型和决策树模型,逻辑斯蒂模型预测价值高、性能指标稳健,其预测精度受试者工作曲线面积为0.91,模型准确率和召回率分别为84%和88%.在乐观情境下,2025年和2030年焦化行业高概率污染地块数量分别为1599块和1695块;在悲观情境下,2025年和2030年焦化行业高概率污染地块数量分别为1671块和1715块.研究结果可为焦化行业企业用地的修复治理和生态环境的宏观决策提供科学依据.     

Effect of bulk density of coking coal on swelling pressure

Coking coals are the important raw materials for the iron and steel industries and play an important role on its sustainable development, especially on the stamp-charging coke making with the characteristics of increasing the bulk density. There is a significance on the reasonable usage of the coking coal resource with the reduced production cost, improved efficiency of the economy to develop the stamp-charging coke making technology. Important effects of the density of coking coal on the coking and caking properties were investigated. In the article, the maximum values of swelling pressure and variation of Laowan gas coal and Xinjian 1/3 coking coal, Longhu fat coal and Didao coking coal, which were mined at Shenyang and Qitaihe respectively, were investigated under different bulk densities during the coking. The results showed that when the values of density increased from 0.85 ton/m³ to 1.05 ton/m³, for the Laowan gas coal, swelling pressure variation and even the maximum value changed slightly. The swelling pressure was 3.63 KPa when the density was improved to 1.05 ton/m³; for the Xinjian 1/3 coking coal, the values of swelling pressure changed significantly and the maximum values was 82.88 KPa with the density improved to 1.05 when the coal was heated to 600℃. The coke porosity, which was investigated by automatic microphotometer, decreased from 47.4% to 33.1% with the increasing of the density from 0.85 ton/m³ to 1.05 ton/m³, and the decreased value was 14.3%. Meanwhile, the pore structures of four cokes were characterized by an optical microscope.     

Effect of bulk density of coking coal on swelling pressure

Coking coals are the important raw materials for the iron and steel industries and play an important role on its sustainable development, especially on the stamp-charging coke making with the characteristics of increasing the bulk density. There is a significance on the reasonable usage of the coking coal resource with the reduced production cost, improved efficiency of the economy to develop the stamp-charging coke making technology. Important effects of the density of coking coal on the coking and caking properties were investigated. In the article, the maximum values of swelling pressure and variation of Laowan gas coal and Xinjian 1/3 coking coal, Longhu fat coal and Didao coking coal, which were mined at Shenyang and Qitaihe respectively, were investigated under different bulk densities during the coking. The results showed that when the values of density increased from 0.85 ton/m³ to 1.05 ton/m³, for the Laowan gas coal, swelling pressure variation and even the maximum value changed slightly. The swelling pressure was 3.63 KPa when the density was improved to 1.05 ton/m³; for the Xinjian 1/3 coking coal, the values of swelling pressure changed significantly and the maximum values was 82.88 KPa with the density improved to 1.05 when the coal was heated to 600°C. The coke porosity, which was investigated by automatic microphotometer, decreased from 47.4% to 33.1% with the increasing of the density from 0.85 ton/m³ to 1.05 ton/m³, and the decreased value was 14.3%. Meanwhile, the pore structures of four cokes were characterized by an optical microscope.     

SMBBR处理焦化废水性能及菌群结构响应关系

采用特异性移动床生物膜反应器（SMBBR）处理焦化废水,连续监测生物反应器处理性能.通过HS-GC/MS和Illumina高通量测序探究污染物降解与生物膜菌群结构的响应关系;利用CCA分析废水变量对微生物菌群结构的影响关系.结果表明,系统稳定运行50d时总酚去除率达96.62%,100d时硫氰化物和氰化物完全降解,其中酚、硫氰化物和氰化物对NH₄⁺-N的降解具有毒性抑制作用.HS-GC/MS结果显示,经过好氧处理后,80%以上的有机物被完全去除,其中包括全部酚、部分含N、O杂环化合物和长链烷烃等.测序结果表明,反应时间的不同,生物膜菌群丰度和多样性存在差异.反应期间Proteobacteria（变形菌门）相对丰度最高（20.57%~34.55%）,促进了苯酚的降解;优势菌属为norank_f_ODP1230B8.23、unclassified_o_Micrococcales、norank_f_Anaerolineaceae;此外,Thauera（陶厄氏菌属）、Ottowia、unclassified_o_Rhizobiales（根瘤菌属）和Thiobacillus（硫杆菌属）为系统中苯酚、SCN^-和CN^-的降解优势菌.CCA分析表明,pH值与Nitrospira（硝化菌属）正相关性最大,有效控制pH值可有助于硝化反应的稳定运行.本文研究结论可为生物膜法处理焦化废水提供理论依据.     

炼焦过程及周边环境颗粒物中水溶性无机离子特征

为明确炼焦过程排放颗粒物及周边环境颗粒物中水溶性无机离子的污染特征,于2012年5月利用改良的标准大体积总悬浮颗粒采样器采集燃烧室废气烟囱排放、焦炉顶无组织排放及焦炉周边环境空气TSP（total suspended particulates,总悬浮颗粒物）样品,使用Staplex234大流量采样器采集焦炉顶无组织排放及焦炉周边环境空气PM_1.4样品,采用ICS-90离子色谱仪测试样品中SO₄2-、NH₄+、Ca2+、Cl-、NO₃-、F-、Mg2+、K+、Na+共9种水溶性无机离子.结果表明:SO₄2-为炼焦过程排放的特征离子.炼焦过程燃烧室废气烟囱排放的TSP中总水溶性无机离子质量浓度最高,为（5 493±901）μg/m3;其次为焦炉顶无组织排放的TSP,其总水溶性无机离子质量浓度为（902±222）μg/m3;焦炉周边环境空气的TSP中总水溶性无机离子质量浓度最低,为（712±288）μg/m3.SO₄2-为燃烧室废气烟囱排放TSP与燃煤锅炉烟气排放颗粒物中共有的主要特征离子,但与燃煤锅炉烟气相比,燃烧室废气烟囱排放的w（SO₄2-）略低,w（F-）则相反.NH₄+较易富集于焦炉顶无组织排放的细颗粒物中,而SO₄2-则较易富集于粗颗粒物中.研究显示,炼焦过程及焦炉周边环境空气颗粒物中9种水溶性无机离子分布特征不同,SO₄2-是燃烧室废气烟囱排放、焦炉顶无组织排放的TSP中质量浓度最高的水溶性无机离子.      

焦化废水活性污泥中降解硫氰化物细菌种群多样性分析

硫氰化物(SCN-)是焦化废水中COD的主要来源之一,其在生物处理工艺好氧段的去除效果直接影响出水的达标排放,活性污泥中的微生物种群在SCN-生物处理中发挥重要作用.以SCN-为唯一碳源和能源驯化活性污泥,研究其对100、300和600 mg·L-1SCN-浓度的去除降解效果,并利用454测序技术解析污泥中降解SCN-的细菌多样性.结果表明,驯化污泥能有效去除100~600 mg·L-1SCN-,SCN-浓度越高,去除速率越高,然而细菌群落多样指数越低;原始污泥和驯化污泥的细菌门类群主要为Proteobacteria、Bacteroidetes、Chlorobi、Planctomycetes、Acidobacteria、Nitrospira、Firmicutes和Unclassified,其中Proteobacteria和Bacteroidetes门占主导地位;Thiobacillus是主要的SCN-降解菌,在3个污泥样品中的丰度分别为3.07%、8.63%和0.27%.Thiobacillus是浓度小于300 mg·L-1SCN-时焦化废水中主要的SCN-降解菌,而在600 mg·L~(-1) SCN-高浓度时低丰度的SCN-降解菌群可能发挥协同降解作用.这些结果为揭示焦化废水处理SCN-污染物的去除机制提供了基础.     

市政污泥接种焦化废水好氧降解能力及微生物群落演替的响应分析

焦化废水是毒性很大的典型工业废水,生物处理过程中需要微生物具备很强的适应能力.以探讨焦化废水对微生物的毒性抑制以及微生物对焦化废水的适应过程为目的,通过于焦化废水原水中接种市政污泥,在考察COD、苯酚、氨氮和硫氰化物等主要污染物指标降解的基础上,运用Illumina高通量测序平台分析降解过程微生物群落组成及多样性变化的响应关系.结果表明,接种了市政污泥的焦化废水培养16 h后COD开始下降,40 h时苯酚降解了97.14%,72 h时硫氰化物开始降解,96 h时硫氰化物浓度低于检测限,氨氮浓度随着硫氰化物的降解而升高.群落测序分析表明,不同培养阶段污泥中微生物表现出群落结构及丰度上的差异:在苯酚降解阶段,苯酚优势降解菌Acinetobacter、Pseudomonas的丰度增大,48 h总相对丰度为13.04%;在硫氰化物降解阶段,Sphingobacterium、Brevundimonas、Lysobacter、Chryseobacterium为主导菌属,96 h时其总相对丰度为16.13%;在144 h阶段,优势菌属则变为Fluviicola、Stenotrophomonas和Thiobacillus,总相对丰度为22.45%.由此认为,市政污泥克服了焦化废水中毒性成分的抑制作用之后能迅速适应环境,表现出微生物群落结构随着废水降解成分的变化而改变,环境因子和降解功能菌之间的竞争是群落结构演变的主要因素.     

深度处理工艺在重钢焦化废水处理中的应用

焦化废水处理中COD及色度问题一直是困扰焦化企业的关键问题,重钢焦化厂成功应用废水深度处理工艺解决了COD及色度的处理问题,确保了重钢新区焦化废水处理系统处理后指标全部达到国家一级排放标准.     

超声-微电解法预处理焦化废水

采用超声-微电解法预处理焦化废水,结果表明,联用处理效果优于超声波法或铁碳微电解法单独处理效果。当反应条件为超声波声功率180 W、曝气量1.5 L/min、投加铁屑量80 g/L、处理时间90 min时,COD去除率可达24%,NH3-N的去除率达30%,挥发酚的去除率达32%。