Coke behavior with H_(2)O in a hydrogen-enriched blast furnace:A review

Hydrogen-enriched blast furnace ironmaking has become an essential route to reduce CO_(2)emissions in the ironmaking process.However,hydrogen-enriched reduction produces large amounts of H_(2)O,which places new demands on coke quality in a blast furnace.In a hydrogen-rich blast furnace,the presence of H_(2)O promotes the solution loss reaction.This result improves the reactivity of coke,which is 20%-30%higher in a pure H_(2)O atmosphere than in a pure CO_(2)atmosphere.The activation energy range is 110-300 kJ/mol between coke and CO_(2)and 80-170 kJ/mol between coke and H_(2)O.CO_(2)and H_(2)O are shown to have different effects on coke degradation mechanisms.This review provides a comprehensive overview of the effect of H_(2)O on the structure and properties of coke.By exploring the interactions between H_(2)O and coke,several unresolved issues in the field requiring further research were identified.This review aims to provide valuable insights into coke behavior in hydrogen-rich environments and promote the further development of hydrogen-rich blast furnace ironmaking processes.

A molecular insight into coke formation process of vacuum residue in thermal cracking reaction

Understanding the coking behaviors has been considered to be really essential for developing better vacuum residue processing technologies.A battery of thermal cracking tests of typical vacuum residue at 410℃ with various reaction time were performed to evaluate the coke formation process.The total yields of ideal components including naphtha,atmospheric gas oil(AGO)and vacuum gas oil(VGO)of thermal cracking reactions increased from 10.89%to 40.81%,and the conversion ratios increased from8.05%to 43.33%with increasing the reaction time from 10 to 70 min.The asphaltene content increased from 12.14%to a maximum of 22.39%and then decreased,and this maximum of asphaltene content occurred at the end of the coking induction period.The asphaltenes during the coking induction period,at the end and after coking induction period of those tested thermal cracking reactions were characterized to disclose the structure changing rules for coke formation process,and the coke formation pathways were discussed to reveal the coke formation process at molecular level.

Role of iron ore in enhancing gasification of iron coke:Structural evolution,influence mechanism and kinetic analysis

The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Classifying coke using CT scans and landmark multidimensional scaling

One factor that limits development of fundamental research on the infuence of coke microstructure on its strength is the difculty in quantifying the way that microstructure is both classifed and distributed in three dimensions.To support such fundamental studies,this study evaluated a novel volumetric approach for classifying small(approx.450μm^(3))blocks of coke microstructure from 3D computed tomography scans.An automated process for classifying microstructure blocks was described.It is based on Landmark Multi-Dimensional Scaling and uses the Bhattacharyya metric and k-means clustering.The approach was evaluated using 27 coke samples across a range of coke with diferent properties and reliably identifed 6 ordered class of coke microstructure based on the distribution of voxel intensities associated with structural density.The lower class(1–2)subblocks tend to be dominated by pores and thin walls.Typically,there is an increase in wall thickness and reduced pore sizes in the higher classes.Inert features are also likely to be seen in higher classes(5–6).In general,this approach provides an efcient automated means for identifying the 3D spatial distribution of microstructure in CT scans of coke.

Experiment and modeling of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites

Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.

Benchmark Dose Assessment for Coke Oven Emissions-Induced Mitochondrial DNA Copy Number Damage Effects

Objective The study aimed to estimate the benchmark dose(BMD)of coke oven emissions(COEs)exposure based on mitochondrial damage with the mitochondrial DNA copy number(mtDNAcn)as a biomarker.Methods A total of 782 subjects were recruited,including 238 controls and 544 exposed workers.The mtDNAcn of peripheral leukocytes was detected through the real-time fluorescence-based quantitative polymerase chain reaction.Three BMD approaches were used to calculate the BMD of COEs exposure based on the mitochondrial damage and its 95%confidence lower limit(BMDL).Results The mtDNAcn of the exposure group was lower than that of the control group(0.60±0.29 vs.1.03±0.31;P<0.001).A dose-response relationship was shown between the mtDNAcn damage and COEs.Using the Benchmark Dose Software,the occupational exposure limits(OELs)for COEs exposure in males was 0.00190 mg/m^(3).The OELs for COEs exposure using the BBMD were 0.00170 mg/m^(3)for the total population,0.00158 mg/m^(3)for males,and 0.00174 mg/m^(3)for females.In possible risk obtained from animal studies(PROAST),the OELs of the total population,males,and females were 0.00184,0.00178,and 0.00192 mg/m^(3),respectively.Conclusion Based on our conservative estimate,the BMDL of mitochondrial damage caused by COEs is0.002 mg/m^(3).This value will provide a benchmark for determining possible OELs.

Orientational Separation of Sulfur in Petroleum Coke by Alkali Calcining and Reflux Washing

The application of high-sulfur petroleum coke after desulfurization in aluminum electrolysis anodes is an important development trend. However, removing sulfur from high-sulfur petroleum coke is still a significant challenge.This study proposes alkali calcining and reflux washing to examine the impacts of temperature, particle size, the mass ratio of Na_(2)CO_(3) to NaOH, and total sodium addition on the desulfurization efficiency and mechanism. The results show that the desulfurization rate increases with increasing temperature, increasing total sodium content, and decreasing particle size. The addition of alkali can significantly reduce the opening-ring reaction temperature of thiophene and convert organic sulfur into inorganic sulfur(Na_(2)S). Three washing methods were compared, and reflux washing was selected to separate inorganic sulfur(Na_(2)S) from calcined petroleum coke. The sulfur content in petroleum coke decreased from 7.29% to 1.90%, with a desulfurization rate of 80.13% under optimal conditions. The petroleum coke was analyzed before and after desulfurization using X-Ray diffraction(XRD), Scanning Electron Microscopy(SEM), Infrared Spectroscopy(IR), Thermogravimetric Analysis and Differential Scanning Calorimetry(TG-DSC), Gaschromatography-mass Spectrometry(GC-MS). The results show that thiophene and benzothiophene in petroleum coke are decomposed and converted into octane and ethyl cyclohexane. These new observations are expected to provide further understanding and guidance for the utilization of highsulfur petroleum coke.

Corrosion of Basic Refractories for Glass Tanks Using Petrol Coke and Countermeasures

Replacing heavy oil with petrol coke can greatly reduce the cost of glass production,but obviously shorten the service life of refractories used in the regenerator checker body of glass tanks.To prolong the service life of the regenerator checker body,the slag chemical composition and alkali-sulfur ratio of glass tanks after using petrol coke and the damage mechanism of the residual magnesia bricks in the regenerator checker body were studied,as well as the corrosion resistance of three magnesia based bricks(direct bonded magnesia chrome bricks,fused rebonded magnesia chrome bricks,and fused rebonded high-purity magnesium aluminate spinel bricks).On this basis,a series of targeted countermeasures were adopted to optimize the configuration of refractories,significantly improving the service life of checker bricks and meeting the requirements of glass industry development.

燃用高碱煤锅炉受热面结焦及其防治研究概述

以准东煤为代表的高碱煤虽储量巨大,但火电机组掺烧高碱煤过程中造成锅炉受热面结焦问题突出,不仅降低锅炉热效率,而且严重威胁机组安全、稳定、经济运行。为解决结焦技术难题,促进高碱煤掺烧利用,对燃用高碱煤锅炉受热面结焦及其防治研究进行了综述。截至目前,国内外围绕燃煤锅炉受热面结焦特征、结焦机理、影响因素、防治措施等已经开展了广泛研究并取得了丰硕的研究成果。在控制燃煤质量、改善锅炉结构、优化锅炉运行等措施基础上,在锅炉受热面制备涂层成为防治结焦的重要技术途径。在未来研究过程中,涂层在具备突出抗结焦性能的同时,须兼具优良的耐高温、抗腐蚀、耐磨损、导热性、热疲劳等综合性能,且具有良好的制备经济性、制备效率,特别是现场适用性。

焦炉煤气脱碳法及甲烷化法制液化天然气的生命周期环境影响分析

作为焦化副产品,焦炉煤气富含氢气和甲烷,采用焦炉煤气制液化天然气(LNG)已成为当前焦炉煤气利用的主要途径之一。为系统评估焦炉煤气制LNG工艺的能源消耗和环境影响,尤其是碳排放,本文采用生命周期评价方法对脱碳法和甲烷化法两种焦炉煤气制LNG工艺进行系统评价。结果表明,无论采用哪种方法,LNG生产阶段均为焦炉煤气制LNG工艺生命周期环境负荷的控制阶段;在脱碳法工艺中,中压蒸汽是环境影响贡献的关键物质,可通过干熄焦回收红焦余热副产蒸汽补充LNG生产消耗来降低环境负荷;在甲烷化工艺中,电力为主要贡献物质,在碳排放中占比41.09%,若采用可再生能源电力(太阳能发电、风电、水电)替代后环境影响显著降低;相比于脱碳法,采用甲烷化工艺环境性能更优,主要源于甲烷增产优势。本文研究结果可从生命周期角度为焦化行业焦炉煤气的综合利用提供理论支持。

煤液化残渣诱导缩聚制备冶金焦的影响因素

煤液化残渣所含沥青质和重油在热解时可产生大量自由基,如不能被及时稳定和缩聚将转化为大量焦油和气体,形成孔隙结构,从而影响所制冶金焦密度。为此,拟引入添加剂诱导其高效缩聚,提高聚合物密度,再经炭化后制备优质冶金焦。通过系统研究不同添加剂(糠醛、甲醇、呋喃和羟基丙酮)、温度(350、400、450、500和550℃)、停留时间(0、30、60和120 min)和添加量(0、4、8和16 g)对所制聚合物缩聚率、结构性质、密度、热稳定性和表面性质影响,获得煤液化残渣诱导缩聚的最优试验条件。在最优条件下,分别探讨所制聚合物和炭化物的表面形貌、微晶结构和元素变化情况,获得煤液化残渣诱导缩聚机理。结果表明,添加剂(糠醛)的诱导缩聚效果最佳,其次是羟基丙酮,因而理想添加剂至少应含有1个醛基或酮基。不同添加剂可促进煤液化残渣缩聚,提高所制聚合物比表面积、孔容、平均孔径和真密度。温度和停留时间对煤液化残渣/糠醛聚合物热稳定性和表面性质影响较大,温度升高和停留时间延长可促进煤液化残渣所含酚类基团和芳香物中H参与缩聚反应,提高聚合物的缩聚程度。煤液化残渣/糠醛(焦炭)整体呈片层密实状,并含更多无定形碳。

燃煤锅炉改燃兰炭燃烧工艺及效益分析

兰炭因热值高、硫含量低的特点被广泛应用于散煤替代,燃煤锅炉改燃兰炭是实现资源合理利用、降低污染物排放和改善企业经济效益的有效途径。以河北某循环流化床锅炉改燃兰炭工程为例,燃烧系统采用掺烧灰渣的方法,解决改燃后机械未完全燃烧导致损失大和物料循环不稳定问题,确定了兰炭和灰渣的最佳掺混比为9∶1;配风系统采用控制总量并降低一次风率的方法,解决兰炭着火困难的问题,确定了最佳一次风比例为55%;换热系统采用增加锅炉尾部受热面的方法,解决因燃料热值提升较大产生的蒸汽超温和锅炉效率下降问题。改燃扩容后锅炉烟尘、SO2和NOx排放分别比原锅炉降低了73%、94%和55%,以原锅炉35 t/h的额定功率运行,每小时节约燃料成本5.51%,产吨蒸汽所需燃料成本降低6.47元。

煤制兰炭过程中挥发性有机污染物和臭氧协同处理机理

为探究低温等离子体联合催化剂载体协同处理煤制兰炭过程中产生的挥发性有机污染物及臭氧,以二甲苯作为目标污染物,选取γ-氧化铝小球为催化剂载体,考察功率、氧通量、二甲苯初始浓度、催化剂载体用量等因素对挥发性有机污染物和臭氧协同处理效果的影响。结果表明:低温等离子体放电功率越大,二甲苯的脱除效果越好;在放电功率为70 W、氧通量为15%、初始浓度为600×10^(-6)时,二甲苯的去除率为64.41%,此时臭氧的产生量为125.21×10^(-6),综合考量在该性能下的协同处理效率最高;在最优低温等离子体性能的条件下,γ-氧化铝载体粒径越小,二甲苯的去除效率越高,协同处理效果最佳,二甲苯总去除率最高可达73.93%,臭氧抑制率最高为66.45%。γ-氧化铝载体对低温等离子体协同处理挥发性有机污染物与臭氧具有一定的促进作用。研究成果可为协同处理挥发性有机污染物提供有效的参考。

高炉喷吹用烟煤配煤炼焦试验研究

为了扩大炼焦煤资源,优化配煤结构,结合烟煤配煤炼焦理论,通过高炉喷吹用烟煤的工业铁桶试验研究,分析了配加烟煤后配合煤的性能变化和所炼焦炭的质量。结果表明:适当增加1/3焦煤、减少气煤配比,烟煤配加质量分数控制在2%~3%,可以有效优化配煤结构,使配合煤的灰分、硫分及挥发分保持在稳定状态,改善焦炭的机械强度、热强度,提高焦炭的块度,同时还可以降低配煤成本,当烟煤配加质量分数为2%时,配煤成本可降低15.60元/t。

不定型煤基活性焦制备及预处理影响研究

我国煤炭燃烧排放大量的SO2和NOx等导致了严重的空气污染,需要寻找一种清洁高效的烟气联合脱硫脱硝技术.煤基活性焦因其脱除效率高,再生能力强等诸多优点备受关注,但目前的研究主要集中在柱状和粉末状活性焦上.为研究大粒径煤基活性焦的制备参数和预处理对活性焦理化特性的影响,对原煤颗粒进行高温空气预氧化处理,并通过炭化-水蒸气活化两步法制备活性焦.结果表明:低温长时间活化可使炭化料内部孔隙充分刻蚀,显著提高比表面积和孔容,以水蒸气作为活化剂有利于微孔和介孔协同发展,适合制备大粒径分级孔结构活性焦.700℃活化3 h制得的府谷煤活性焦比表面积为429.54 m^(2)/g,介孔占比27.80%;850℃活化3 h制得的大同煤活性焦比表面积为892.20 m^(2)/g,介孔占比21.46%.高温空气预氧化能够改变原煤内部结构,对府谷煤颗粒在200℃下预氧化15 h后,氧化煤内部成分和结构基本稳定,脂肪结构被消耗的同时生成了大量含氧官能团.预氧化处理对炭化过程的影响较为显著,氧化煤在炭化过程中热塑性特征显著降低,减少了焦油对孔隙的堵塞,此外,含氧官能团的交联作用也促进了煤中大分子的缩聚和孔隙的形成,从此促进初步孔隙的发展.虽然预氧化使得活性焦的比表面积和孔容都有所增大,但活化剂和样品之间的成孔路径未产生改变.

酸化后焦煤表面性和孔隙性变化对吸附热的影响

目的为了探究酸化后焦煤的表面性和孔隙性变化对其吸附热的影响,方法选取山西古交矿区焦煤为研究对象,利用盐酸(HCl)和氢氟酸(HF)酸化处理,采用接触角法、低温液氮吸附法和微量热法等测试方法,对比分析了酸化前后焦煤的煤-水接触角、表面张力、孔隙结构等变化,并探讨了这些变化对吸附热的影响机制。结果酸化后焦煤的平均煤-水接触角由75.10°增至80.11°,平均表面张力由44.44 mJ/m^(2)减至39.48 mJ/m^(2),亲水性减弱;酸化后焦煤的总孔容、中孔孔容、比表面积和平均孔径均增大,而微孔和大孔的孔容及比表面积均减小,表明矿物质脱除有利于微孔向中孔转化;同等压力下,随着温度升高,分子热运动加强,分子能量突破固体表面势垒,气体分子成为游离态,导致原煤和脱灰煤的积分吸附热和微分吸附热减小,且脱灰煤的吸附热高于原煤的。结论矿物质会减弱焦煤对气体的吸附能力,且占据焦煤表面的吸附位。因此,酸化后矿物质的脱除导致焦煤表面的吸附位增加,是引起吸附热增大的主要原因。

离子色谱测定无糖可乐中的甜蜜素

本文对无糖可乐中的甜蜜素含量测定方法进行研究,优化了色谱分离条件,建立了离子交换-电导法测定无糖可乐中的甜蜜素的方法。该方法使用的色谱柱是Thermo IonPac AG11-HC(50mm×4mm)保护柱以及Thermo IonPac AS11-HC(250mm×4mm)分离柱,KOH梯度淋洗,抑制电导检测。结果表明,甜蜜素在0.112mg/L~112mg/L时有良好的线性关系,相关系数在0.999以上;方法检出限为0.05mg/L,系统相对偏差在2%以内,回收率98.22%~103.9%。该方法操作简便,分析快速,重现性好,结果准确、可靠,适用于无糖可乐中甜蜜素的含量测定。

不同有机肥对土壤及核桃果实品质的影响

为探究“辽宁1号”核桃较适宜的有机肥,在河北省隆尧县红沙峪生态农业科技有限公司核桃园以10年生“辽宁1号”核桃树为试验材料,利用半焦肥、鸡粪及生物菌肥3种有机肥进行施肥处理,检测不同有机肥对土壤性状、核桃产量和品质的影响。结果表明,生物菌肥(2.5 kg/株)能显著提高种仁黄酮含量;鸡粪(40 kg/株)能显著提高种仁Fe、Zn含量以及土壤速效磷、速效钾含量;5.0 kg/株半焦肥能显著提高种仁多酚、土壤有机质含量;10.0 kg/株半焦肥施肥能显著提高青果的横径,坚果的单果质量、纵径、横径、侧径,种仁的脂肪、K、Ca、Mn、Cu含量以及土壤全磷含量。10.0 kg/株半焦肥在相关果实品质方面的综合效果最好,而5.0 kg/株半焦肥的经济效益最高。

延迟焦化装置酸性水除油脱焦粉技术改造

某石化公司1.2Mt/a延迟焦化装置在生产运行过程中存在分馏塔顶酸性水带油、带焦粉问题,在焦炭塔预热,污油、废渣回炼时尤为明显。分析原因为加工原料组成变化、酸性水量增加等导致分馏塔顶酸性水发生乳化、沉降时间不足,影响下游酸性水汽提装置的稳定运行。为解决以上问题,通过实施技术改造,在原分馏塔顶油水分离罐后增上一座酸性水沉降罐,将酸性水停留时间由1.10~2.56h增加至3.50~8.10h;在新增酸性水沉降罐后增加一台自动反冲洗过滤器,脱除酸性水中≥10μm的焦粉颗粒。技术改造实施完成投用后标定结果表明:酸性水中油含量从882mg/L下降至162mg/L,使油水充分分离,除油率达到81.63%;≥10μm的焦粉颗粒含量从463mg/L下降至9mg/L,脱除率达到98.06%,有效降低了酸性水油含量和焦粉颗粒含量,为下游酸性水汽提装置的稳定运行创造了条件。