Effect of mass fraction of long flame coal on swelling pressure and microstructures of cokes

Long flame coal are abundant and widely distributed in China, but the resource utilization is quite low, the production efficiency is not high. Stamp-charging coke making technology can bend some long flame coal, which can reduce production cost and expand the coking coal resources. The long flame coal of different mass fraction is added into prime coking coal including fat coal from Longhu, 1/3 coking coal from Xinjian and coking coal from Didao in experiment. The swelling pressure is tested on-line detection using pressure sensor in coke making process, and the pores are observed by scanning electron microscopy. The results show that, the swelling pressure first increase and then decrease with the temperature increased and the maximum swelling pressure reduces gradually with mass fraction of the Long flame coal from Shenmu increased in coke making process. The SEM images of resultant coke display that the coke get more and more loose and the amount of pores is increased with mass fraction of the long flame coal from Shenmu increased. The amount pores and the pore diameter both is minimum for coking coal from Didao as prime coking coal under the same fraction of long flame coal.     

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.     

我国常规焦炉危险废物产生和利用处置现状及对策

我国是世界上最大的焦炭生产国和供应商,以常规焦炉炼焦工艺为主,常规焦炉会排放气体、液体和固体污染物.常规焦炉危险废物的产生现状是种类多、产生工艺节点多样、产生量大、污染物种类繁杂、对生态环境和人体的潜在危害大.对高附加值的高温煤焦油采取深加工的方式生产多种化工原料,脱硫废液的利用方式是提取单品精盐和制酸,其他低附加值的常规焦炉危险废物回配煤单元炼焦.当前,我国常规焦炉危险废物利用处置存在3个问题:①部分高温煤焦油深加工技术不属于清洁生产技术;②脱硫废液提取的盐缺乏污染控制标准或技术规范,脱硫废液制酸设备稳定运行难度较大;③危险废物回配煤单元可能引起炼焦产品质量下降和环境风险增大.针对我国常规焦炉危险废物产生和利用处置存在的问题,建议从3个方面提高炼焦危险废物利用率和加强安全处置:①遵循《国家危险废物名录》中"危险废物豁免管理清单"利用环节豁免条件,采取先进的清洁生产技术,促进高温煤焦油利用;②制定以脱硫废液为原料提取盐的污染控制标准或技术规范,将小规模企业产生的脱硫废液"点对点"集中输送至专门利用脱硫废液制酸的企业生产硫酸,开发易于推广、平稳高效连续运行和自动化控制的提盐和制酸技术,提高脱硫废液利用水平;③常规焦炉危险废物返回配煤工序炼焦时应精准管控,确保炼焦产品质量,防范环境风险.      

吸附法处理焦化废水的研究进展

焦化废水是煤制焦炭、煤气净化及焦化产品回收过程中产生的废水,其成分复杂多变,属于难处理的工业废水。介绍了近年来焦化废水的吸附处理技术,包括常用吸附剂及吸附法与其它方法联用的应用情况。     

焦化废水生化处理研究新进展

焦化废水是炼焦、煤气净化及焦化产品回收过程中产生的废水。总结了近几年焦化废水生化处理技术与工艺及其影响因素,并结合近年来环境生物技术的前沿,提出了焦化废水生化处理技术的发展方向。     

典型焦化厂大气挥发性有机物排放表征分析

焦化行业是我国重要工业类别,但因其工艺过程复杂,所以VOCs（挥发性有机物）排放特征尚不明确.以典型机械焦化厂为研究对象,对焦炉烟囱、推焦、装煤和焦炉顶等不同排放环节进行采样,并利用GC/MS（气相色谱质谱联用仪）进行多物种分析,并对焦化厂排放VOCs的OFP（生成O₃的潜势）进行探索性研究.结果表明:①焦化厂排放的VOCs包括烷烃、烯烃、炔烃、芳香烃、卤代烃和含氧VOCs等六大类,共90多个物种.②不同环节排放的ρ（VOCs）差异显著,其中,焦炉烟囱ρ（VOCs）排放量（87.1 mg/m3）最大,其次为推焦（4.0 mg/m3）、装煤（3.3 mg/m3）和焦炉顶（1.1 mg/m3）.③不同环节排放的VOCs种类不同,但均以烷烃和烯烃为主,其中,焦炉烟囱排放的烯烃最多（占比达66%）,装煤和推焦排放的则以烷烃为主（占比分别为42%和36%）,焦炉顶排放的烷烃和烯烃相近（占比分别为31%和29%）.④基于排放特征和最大增量反应活性法研究发现,焦炉烟囱是焦化厂VOCs减排的重点环节,烯烃是重点减排的物种,特别是乙烯、丙烯、丁烯和1,3-丁二烯等,但乙醛、苯、甲苯等也不容忽视.研究显示,以乙烷/丙烷/乙烯（三者质量浓度之比）为指标,可明显区分焦炉烟囱、推焦、装煤和焦炉顶等不同环节的VOCs排放.      

炼焦过程中单环芳烃排放及源特征

通过不锈钢采样罐采样和液氮预浓缩/气相色谱/质谱系统分析,研究我国山西某地的土法炼焦和机械炼焦生产过程中单环芳烃(MAHs)的排放情况.炼焦过程MAHs以苯、甲苯、(间+对)-二甲苯为主要成分,苯和总MAHs浓度在土法炼焦烟气中最高达3421.0μg/m3和4865.9μg/m³,在机械炼焦无组织排放气体和烟气中分别为548.7μg/m³、1054.8μg/m³和1376.4μg/m³、1819.4μg/m³.焦炭生产过程中MAHs浓度变化显著:土法炼焦过程MAHs前期释放浓度高于后期;机械炼焦无组织排放MAHs在装煤和出焦时明显升高;而机械炼焦烟气中则是装煤时最高,出焦时最低.苯、甲苯、乙苯和二甲苯(BTEX)散点图和相关性分析显示机械炼焦释放MAHs主要来自煤的高温分解,而土法炼焦中MAHs释放则可能除焦煤不完全燃烧释放外还受别的因素影响.苯/甲苯/乙苯/二甲苯比值(B/T/E/X)特别是苯/乙苯(B/E)值显示炼焦释放的MAHs具有不同于其它来源的特征.     

废塑料配煤炼焦机理研究及进展

基于高温干馏技术,利用煤与废塑料共焦化技术处理废塑料可将其转化为焦化产品,实现废塑料的资源化利用和无害化处理。在此从分析煤与废塑共焦化机理方面,探究共焦化对炼焦的影响,表明添加一定比例废塑料可略提高焦炭质量,增加焦油及焦炉煤气产率,同时降低化合水产率,说明废塑料的添加提高了煤中氢的利用率。     

炼焦炉周边土壤、降尘和熄焦渣中水溶性离子的分布特征

为了明确炼焦炉周边土壤、降尘和熄焦渣中水溶性离子的分布特征,采集焦化厂厂区内土壤、降尘、熄焦渣及厂区外土壤样品,利用美国戴安公司ICS-90型离子色谱仪测定样品中SO₄2-、NO₃-、Cl-、F-、NH₄+、Na+、Ca2+、K+、Mg2+ 9种水溶性离子。结果表明:炼焦炉周边土壤、降尘和熄焦渣中总水溶性离子质量浓度分别为1.65,5.27,2.19 g/kg。炼焦炉周边土壤中SO₄2-和NH₄+的变异系数分别为84.22%和51.17%,说明炼焦炉周边土壤受到炼焦过程排放污染物的影响不同,且厂区内土壤更易受到炼焦过程的影响。燃烧室废气排放烟囱旁和熄焦塔南降尘中NO₃-/SO₄2-分别为0.46和0.03,说明炼焦炉周边降尘也受到炼焦过程排放污染物的影响。熄焦塔南降尘中总水溶性离子和SO₄2-的质量分数是燃烧室废气烟囱旁降尘的6.99,18.44倍,熄焦渣和熄焦塔南降尘水溶性离子分布特征基本相同,二者之间存在明显相关性。SO₄2-是炼焦炉周边土壤、降尘和熄焦渣中质量分数最高的水溶性离子,因此建议加强炼焦过程颗粒物和SO₂排放的控制。     

Effects of atamp-charging coke making on strength and high temperature thermal properties of coke

The stamp-charging coke making process has some advantages of improving the operation environment, decreasing fugitive emission, higher gas collection efficiency as well as less environmental pollution. This article describes the different structure strength and high temperature thermal properties of 4 different types of coke manufactured using a conventional coking process and the stamp-charging coke making process. The 4 kinds of cokes were prepared from the mixture of five feed coals blended by the petrography blending method. The results showed that the structure strength indices of coke prepared using the stamp-charging coke method increase sharply. In contrast with conventional coking process, the stamp-charging process improved the coke strength after reaction but had little impact on the coke reactivity index.     

Effects of atamp-charging coke making on strength and high temperature thermal properties of coke

The stamp-charging coke making process has some advantages of improving the operation environment, decreasing fugitive emission, higher gas collection efficiency as well as less environmental pollution. This article describes the different structure strength and high temperature thermal properties of 4 different types of coke manufactured using a conventional coking process and the stamp-charging coke making process. The 4 kinds of cokes were prepared from the mixture of five feed coals blended by the petrography blending method. The results showed that the structure strength indices of coke prepared using the stamp-charging coke method increase sharply. In contrast with conventional coking process, the stamp-charging process improved the coke strength after reaction but had little impact on the coke reactivity index.     

废塑料与炼焦配煤共焦化产物的分析

利用2kg模拟焦炉，进行了首钢炼焦配煤与北京市石景山区生活垃圾中的废塑料的共焦化实验。研究结果表明，添加废塑料有提高焦油收率和减少水的收率的趋势；但添加废塑料对成焦率、焦油产率及水产率的影响随废塑料处理方法和废塑料添加比例的不同而有差异；采用废塑料型煤或废塑料型煤破碎物与配煤共焦化在提高废塑料添加比例方面具有较大优势。     

焦化厂多环芳烃成分谱特征的研究

在焦炉顶端采集颗粒物样品,用气相色谱-质谱联用技术测定了其中13种多环芳烃的含 量.通过与燃煤烟尘和交通隧道中BaP含量的比较,说明焦化作业是造成多环芳烃污染的重要 污染源之一.将分析结果进行归一化处理后,确定了焦化厂多环芳烃成分谱,这一成分谱在轮 廓特征和特征比值方面都表现出与燃煤型污染的相似性,而与交通型污染差别较大.     

煤焦化生产过程甲烷排放初步研究

本研究选取山西省具有代表性的焦化厂,通过在废气排放烟囱上采集燃烧室废气和装煤/出焦废气,初步研究了煤焦化过程甲烷排放特征。结果显示燃烧室废气中CH4占∑(CH4+NMHC)的比例远高于装煤和出焦废气。基于EPA AP-42排放因子的计算方法,煤焦化三个工段的CH4排放因子为228.5±56.1g/t。结合中国机械炼焦炉焦炭产量,2004年中国机械炼焦CH4排放为0.03Tg/a,占中国总CH4排放的0.1%,可能是山西省除煤炭开采外的重要甲烷排放源,该值还需再进一步的工作中完善和验证。     

酸焦油配煤研究与应用

为解决酸焦油的处理的问题,梅钢通过配煤炼焦试验,考察酸焦油配煤对配煤质量的影响和焦炭质量的影响,试验结果显示酸焦油配比为0.5%时,焦炭质量有所提高.通过开发酸焦油配煤生产工艺,并应用于生产实践,达到了回收利用和控制污染的目的.     

煤焦化过程中颗粒物和二氧化硫的释放

选择山西省某地的四个土焦炉、两个热回收焦炉和两个机焦炉开展焦炉顶空气和烟气中颗粒物和SO2研究。结果显示在正常工作条件下热回收焦炉顶空气中颗粒物和SO2浓度最小,其次是机焦炉,土焦炉顶最高。机焦炉和热回收焦炉顶污染物浓度在出焦和装煤时明显升高。土焦炉烟气中颗粒物排放浓度和排放速率明显高于热回收焦炉和机焦炉;各种炉型烟气中SO2浓度差别较小,排放速率以机焦炉最高;土焦炉的烟尘和二氧化硫吨焦排放量最高,而机焦炉和热回收焦炉由于环保设备的使用显著降低。生产过程污染物释放显示机焦炉和热回收焦炉的颗粒物和SO2释放主要来源于焦化过程和熄焦过程。由吨焦排放量估计炼焦烟尘和二氧化硫对全国的烟尘和二氧化硫排放贡献小于5%,但对山西省的贡献接近15%和30%,控制炼焦污染对当地环境改善具有重要意义。     

焦油渣和煤沥青配煤炼焦处置实验研究

通过对焦油渣、煤沥青开展配煤捣固炼焦实验,分别分析不同炼焦残渣配比下,焦炭成分的变化,确定其较优掺入比例,并分析残渣对焦炭和尾气中多环芳烃、重金属含量的影响。结果表明,焦油渣掺入比例为4.5%,煤沥青掺入比例为6%是较为适宜的。此条件下,焦炭中重金属含量较高,进入到尾气中的部分有限,而多环芳烃含量极少,大部分都进入到尾气中,故炼焦尾气需要经冷凝、过滤和吸附净化后再排放。     

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.      

焦化厂区空气中SO2和颗粒物的分布及暴露评价研究

对中国山西的土焦炉、热回收焦炉、机焦炉炉顶及周围环境进行采样监测,大型机焦炉颗粒物单位排放浓度高于土焦炉和热回收焦炉,同时超过《炼焦炉大气污染物排放标准》(GB 16171-1996)中国家二级标准限值3.5 mg/m3.机焦炉炉顶在出焦环节超过国家污染物排放标准的5倍.在此种污染物暴露的环境下长期工作生活,对人的健康会造成很大的危害.因此看出全国焦化行业存在着污染物排放治理问题、环保设备更新应用问题以及焦化工人的身体健康问题.     

焦炉烟气中二（口恶）英类物质排放水平研究

二噁英和类二噁英多氯联苯属于《关于持久性有机污染物的斯德哥尔摩公约》规定的非故意产生的持久性有机物,统称为二噁英类物质.焦化生产过程中具备二噁英类物质生成所需的前体物、温度、催化剂等条件,但目前国内外对焦化行业焦炉烟气二噁英类物质排放研究仍属空白,为进一步明确焦化行业排放水平和影响因素,针对性地提出行业减排和控制措施,利用高分辨气相色谱-高分辨质谱法对4个不同规模的典型焦化企业焦炉烟气中二噁英类物质排放情况进行现场采样和实验室分析.结果表明,二噁英类物质毒性当量(以WHO-TEQ计)范围为3.9~30.0 pg·m-3,处于较低水平,检出较多的PCDD/Fs同系物主要是高氯代的.另外,烟气中此类物质的排放量与焦化生产工艺关系密切,捣鼓炼焦、较高的炭化室高度有利于减少二噁英类物质的排放.