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.

Effect of sulfur impurity on coke reactivity and its mechanism

Effect of sulfur impurity on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and impurities doping. And its mechanism was discussed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results show that sulfur has strong catalysis on both air and CO2 reactivity of coke in the case of no other impurity interference. Its catalysis is probably realized by triggering organic sulfur→H2S→SO2→COS and elemental sulfur (Sx)→SO2 and organic sulfur→H2S→COS→Sx→C2S→COS reaction systems during coke?O2 and coke?CO2 reactions, respectively, which are partly circular with functions of increasing carbon consumption and enlarging coke specific surface area.

SO_2 emission characteristics from co-firing of petroleum coke and coal in circulating fluidized bed

Combustion and sulfur retention experiments of mixed fuel of petroleum cokeand coal were conducted on a pilot-scale circulating fluidized bed (CFB) combustor with the thermalinput of 0. 6 MW. The effects of several parameters, such as the primary air percentage, excess aircoefficient, bed temperature, Ca/S molar ratio and mass ratio of petroleum coke to coal on SO_2emission were verified. Experimental results show that when the ratio of petroleum coke to coal inthe mixed fuel increases, the SO_2emission increases. The maximum SO_2 emission appears when purecoke burns. The SO_2 concentration in flue gas reduces with the increase in the primary airpercentage, excess air coefficient and Ca/S molar ratio for all kinds of fuel mixtures. Therangebetween 830 t and 850 t is the optimal temperature for sulfur retention during co-firing ofpetroleum coke and coal with the mass ratio R of 1 and 3 in CFB.

关于美国西方化学技术EDC裂解炉炉管结焦问题的探讨

针对某个采用美国西方化学技术的EDC裂解装置,分析了在高负荷运行条件下影响EDC裂解炉炉管结焦形成的主要7个相关因素,并总结了相应的控制措施。通过合理的控制,达到了延长裂解炉良性运行周期、控制氯乙烯产品品质及相关单耗的目的。

Thermal stable Pt clusters anchored by K/TiO_(2)—Al_(2)O_(3)for efficient cycloalkane dehydrogenation

Catalytic dehydrogenation of cycloalkanes is considered a valuable endothermic process for alleviating the thermal barrier issue of hypersonic vehicles.However,conventional Pt-based catalysts often face the severe problem of metal sintering under high-temperature conditions.Herein,we develop an efficient K_(2)CO_(3)-modified Pt/TiO_(2)—Al_(2)O_(3)(K—Pt/TA)for cycloalkane dehydrogenation.The optimized K—Pt/TA showed a high specific activity above 27.9 mol·mol^(-1)·s^(-1)(H_(2)/Pt),with toluene selectivity above 90.0%at 600℃with a high weight hourly space velocity of 266.4 h^(-1).The introduction of alkali metal ions could generate titanate layers after high-temperature hydrogen reduction treatment,which promotes the generation of oxygen vacancy defects to anchored Pt clusters.In addition,the titanate layers could weaken the surface acidity of catalysts and inhibit side reactions,including pyrolysis,polymerization,and isomerization reactions.Thus,this work provides a modification method to develop efficient and stable dehydrogenation catalysts under high-temperature conditions.

Metagenomic Insight Reveals the Microbial Structure and Function of the Full-Scale Coking Wastewater Treatment System:Gene-Based Nitrogen Removal

Microbial communities play crucial roles in pollutant removal and system stability in biological systems for coking wastewater(CWW)treatment,but a comprehensive understanding of their structure and functions is still lacking.A five month survey of four sequential bioreactors,anoxic 1/oxic 1/anoxic 2/oxic 2(A1/O1/A2/O2),was carried out in a full-scale CWW treatment system in China to elucidate operational performance and microbial ecology.The results showed that A1/O1/A2/O2 had excellent and stable performance for nitrogen removal.Both total nitrogen(TN;(17.38±6.89)mgL1)and ammonium-nitrogen(NH4 t-N;(2.10±1.34)mg·L^(-1))in the final biological effluent satisfied the Chinese national standards for CWW.Integrated analysis of 16S ribosome RNA(rRNA)sequencing and metagenomic sequencing showed that the bacterial communities and metagenomic function profiles of A1 and O1 shared similar functional structures,while those of A2 significantly varied from those of other bioreactors(p<0.05).The results indicated that microbial activity was strongly connected with activated sludge function.Nitrosospira,Nitrosomonas,and SM1A02 were responsible for nitrification during the primary anoxic-oxic(AO)stage and Azoarcus and Thauera acted as important denitrifiers in A2.Nitrogen cycling-related enzymes and genes work in the A1/O1/A2/O2 system.Moreover,the hao genes catalyzing hydroxylamine dehydrogenase(EC 1.7.2.6)and the napA and napB genes catalyzing nitrate reductase(EC 1.9.6.1)played important roles in the nitrification and denitrification processes in the primary and secondary AO stages,respectively.The mixed liquor suspended solids(MLSS)/total solids(TS),TN removal rate(RR),total organic carbon(TOC)(RR),and NH_(4)^(+)t-N(RR)were the most important environmental factors for regulating the structure of core bacterial genera and nitrogen-cycling genes.Proteobacteria were the potential main participants in nitrogen metabolism in the A1/O1/A2/O2 system for CWW treatment.This study provides an original and comprehensive understanding of the microbial community and functions at the gene level,which is crucial for the efficient and stable operation of the full-scale biological process for CWW treatment.

Steam reforming of acetic acid over Ni/biochar of low metal-loading:Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.

Effect of Calcined Temperature on Coke Deposition for Autothermal Reforming of Methane with Ni-Cu Catalyst

Ni-Cu/ZrO2-CeO2-Al2O3 catalysts were prepared by co-precipitation method at pH=9 and using Na2CO3 as the precipitant. The Ni loading （mass fraction） of the catalysts was 10%. The catalysts were characterized by X-ray diffraction, temperature-programmed oxidation （TPO）, scanning electron microscope （SEM）, and X-ray photoelectron spectroscopy （XPS）. The effects of calcined temperature of support on coke deposition were studied. TPO, SEM and XPS results indicated there was no peak of higher temperature oxygen consumption on Ni-Cu/ZrO2-CeO2-Al2O3 catalyst （support was calcined at 800 ℃）, which could lead to the deactivation of the catalyst. The carbon species were carbonate and inactive carbon （filamentous carbon species） on the surface of catalyst reacting for 40 h which perhaps led to the deactivation of the catalyst.

焦炉边火道温度低的原因分析及处理方案

为解决安泰集团焦化厂二炼焦车间JN60型焦炉出现的边火道温度低,个别火道窜漏导致燃烧不正常的问题。通过现场了解边火道温度现状,从数据出发分析出现此情况的原因是管砖破裂。采用更换管砖和喷补灌浆处理的方法,解决了边火道温度低的问题。为同行业同类型焦炉提供技术参考和借鉴。

Regeneration of catalysts deactivated by coke deposition:A review

In industrial catalytic processes,coke deposition can cause catalyst deactivation by covering acid sites and/or blocking pores.The regeneration of deactivated catalysts,thereby removing the coke and simultaneously restoring the catalytic activity,is highly desired.Despite various chemical reactions and methods are available to remove coke,developing reliable,efficient,and economic regeneration methods for catalytic processes still remains a challenge in industrial practice.In this paper,the current progress of regeneration methods such as oxidation(air,ozone and oxynitride),gasification(carbon dioxide and water steam),and hydrogenation(hydrogen)is reviewed,which hopefully can shed some light on the design and optimization of catalysts and the related processes.

Treatment of coke plant wastewater by SND fixed biofilm hybrid system

In this article, coke plant wastewater was treated by a simultaneous nitrifying and denitrifying （SND） fixed biofilm hybrid system. The results showed that suitable parameters of the system were important for the performance of the bio-degradation system. The chemical oxygen demand （COD） removal efficiency in this system was satisfactory, higher than 94%, and ammonia nitrogen was higher than 95%. The effluent COD concentration could meet the discharge standard, except for very few situations. The results showed that a sufficient carbon source was important for making ammonia nitrogen concentration meet the discharge standard. Then the TiN removal efficiency in this system can be brought higher than 94%. Dissolved oxygen （DO） is very important to the performance of the SND bio-degradation system, and the suitable DO is about 3.5-4.0 mg/L at the forepart of reactor. In addition, the performance of the system was almost not affected by pH value. The results show that the system is feasible to treat coke plant wastewater.

Gasification kinetics of bulk coke in the CO2/CO/H2/H2O/N2 system simulating the atmosphere in the industrial blast furnace

The gasification characteristics and gasification kinetics of coke in complex CO2/CO/H2/H2O/N2 systems similar to the gas system of industrial blast furnace (BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model (RPM), Volumetric Model (VM), and Grain Model (GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples (Coke Reaction Index (CRI)>50) is due to the high Fe2O3 in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.