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.

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.

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.

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.

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.

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.

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.

Effect of CO_2 and H_2O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO_2 and H_2O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO_2 and H_2O using high temperature gas–solid reaction apparatus over the range of 950–1250°C were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H_2O is about 1.3–6.5 times that with CO_2 in the experimental temperature range. At the same temperature, the endothermic effect of coke with H_2O is less than that with CO_2. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO_2 and H_2O are 169.23 kJ ·mol-1 and 87.13 kJ·mol^(-1), respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.

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.

Effect of Cr2O3 addition on oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets with simulated coke oven gas

The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.

Effect of physical disturbance on the structure of needle coke

Through different preparation technology, this paper reports that the needle coke is prepared with coal-tar pitch under the effect of magnetic field and ultrasonic cavitation. It studies the effect of physical disturbance on the structure of needle coke. The structure of needle coke is characterized by scanning electron microscope and x-ray diffractometer, and the influence mechanism is analysed. Results showed that the structure and property of needle coke could be effectively improved by magnetic field and ultrasonic cavitations, such as degree of order, degree of graphitization and crystallization. Comparatively speaking, the effect of magnetic field was greater. The graphitization degree of needle coke prepared under the effect of magnetic field is up to 45.35%.

Prediction of Coke Yield of FCC Unit Using Different Artificial Neural Network Models

In fluid catalytic cracking(FCC) unit, it is greatly important to control the coke yield, since the increase of coke yield not only leads to the reduction of total liquid yield, but also affects the heat balance and operation of FCC unit. Consequently, it is significant to predict the coke yield accurately. The coke formation and burning reactions are affected by many parameters which influence each other, so it is difficult to establish a prediction model using traditional models. This paper combines the industrial production data and establishes a generalized regression neural network(GRNN) model and a back propagation(BP) neural network model to predict the coke yield respectively. The comparison and analysis results show that the accuracy and stability of the BP neural network prediction results are better than that of the GRNN. Then, the particle swarm optimization to optimize BP neural network(PSO-BP) and genetic algorithm to optimize the BP neural network(GA-BP) were further used to improve the prediction precision. The comparison of these models shows that they can improve the prediction precision. However, considering the accuracy and stability of the prediction results, the GA-BP model is better than PSO-BP model.

Effect of Ni loadings on the activity and coke formation of MgO-modified Ni/Al_2O_3 nanocatalyst in dry reforming of methane

MgO-modified Ni/Al2O3 catalysts with different Ni loadings were prepared and employed in dry reforming of methane （DRM）. The effect of Ni loadings on the activity and coke formation of Ni/MgO-A1203 catalysts were investigated. The synthesized catalysts were characterized by XRD, N2 adsorption-desorption, SEM, TPO and TPR techniques. The obtained results showed that increasing nickel loading decreased the BET surface area and increased the catalytic activity and amount of deposited carbon. In addition, the effect of gas hourly space velocity （GHSV） and feed ratio were studied.

Batch methanogenic fermentation experiments of wastewater from a brown coal low-temperature coke plant

Coke plant effluents with high contents of organic compounds are mainly treated by biological aerobic fermentation after physical pre-treatment. In this study, a brown coal condensate wastewater from a low temperature coking process was fermented under methanogenic conditions in discontinuous experiments. By this fermentation, acetate, propionate, and the main polyphenolic compounds （catechol, resorcinol and hydroquinone） were degraded to a level below the detection limit. The COD was reduced by 72% with a residual concentration of 2.1 g/L. This anaerobic fermented wastewater had a residual BOD5 of 0.66 g/L and 2.2 L CH4 were formed per litre of wastewater. An abiotic pre-treatment for this wastewater with air had a negative effect on the COD reduction and decrease of colour on the methanogenic fermentation due to the autoxidation of polyphenolic compounds to humic-like compounds. This study showed that methanogenic fermentations in the treatment sequence of brown coal coking wastewaters could reduce energy consumption for aeration in further treatment processes and had the potential for a better effluent quality due to a less formation of recalcitrant humic-like compounds.