Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Structural properties of residual carbon in coal gasification fine slag and their influence on flotation separation and resource utilization:A review

Coal gasification fine slag(FS)is a typical solid waste generated in coal gasification.Its current disposal methods of stockpil-ing and landfilling have caused serious soil and ecological hazards.Separation recovery and the high-value utilization of residual carbon(RC)in FS are the keys to realizing the win-win situation of the coal chemical industry in terms of economic and environmental benefits.The structural properties,such as pore,surface functional group,and microcrystalline structures,of RC in FS(FS-RC)not only affect the flotation recovery efficiency of FS-RC but also form the basis for the high-value utilization of FS-RC.In this paper,the characteristics of FS-RC in terms of pore structure,surface functional groups,and microcrystalline structure are sorted out in accordance with gasification type and FS particle size.The reasons for the formation of the special structural properties of FS-RC are analyzed,and their influence on the flotation separation and high-value utilization of FS-RC is summarized.Separation methods based on the pore structural characterist-ics of FS-RC,such as ultrasonic pretreatment-pore-blocking flotation and pore breaking-flocculation flotation,are proposed to be the key development technologies for improving FS-RC recovery in the future.The design of low-cost,low-dose collectors containing polar bonds based on the surface and microcrystalline structures of FS-RC is proposed to be an important breakthrough point for strengthening the flotation efficiency of FS-RC in the future.The high-value utilization of FS should be based on the physicochemical structural proper-ties of FS-RC and should focus on the environmental impact of hazardous elements and the recyclability of chemical waste liquid to es-tablish an environmentally friendly utilization method.This review is of great theoretical importance for the comprehensive understand-ing of the unique structural properties of FS-RC,the breakthrough of the technological bottleneck in the efficient flotation separation of FS,and the expansion of the field of the high value-added utilization of FS-RC.

Multiscale analysis of fine slag from pulverized coal gasification in entrained-flow bed

Fine slag(FS)is an unavoidable by-product of coal gasification.FS,which is a simple heap of solid waste left in the open air,easily causes environmental pollution and has a low resource utilization rate,thereby restricting the development of energy-saving coal gasification technologies.The multiscale analysis of FS performed in this study indicates typical grain size distribution,composition,crystalline structure,and chemical bonding characteristics.The FS primarily contained inorganic and carbon components(dry bases)and exhibited a"three-peak distribution"of the grain size and regular spheroidal as well as irregular shapes.The irregular particles were mainly adsorbed onto the structure and had a dense distribution and multiple pores and folds.The carbon constituents were primarily amorphous in structure,with a certain degree of order and active sites.C 1s XPS spectrum indicated the presence of C–C and C–H bonds and numerous aromatic structures.The inorganic components,constituting 90%of the total sample,were primarily silicon,aluminum,iron,and calcium.The inorganic components contained Si–O-Si,Si–O–Al,Si–O,SO_(4)^(2−),and Fe–O bonds.Fe 2p XPS spectrum could be deconvoluted into Fe 2p_(1/2) and Fe 2p_(3/2) peaks and satellite peaks,while Fe existed mainly in the form of Fe(III).The findings of this study will be beneficial in resource utilization and formation mechanism of fine slag in future.

Effective separation of coal gasification fine slag: Role of classification and ultrasonication in enhancing flotation

Effective separation of residual carbon and ash is the basis for the resource utilization of coal gasification fine slag(CGFS).The conventional flotation process of CGFS has the bottlenecks of low carbon recovery and high collector dosage.In order to address these issues,CGFS sample taken from Shaanxi,China was used as the study object in this paper.A new process of size classification-fine grain ultrasonic pretreatment flotation(SC-FGUF)was proposed and its separation effect was compared with that of wholegrain flotation(WGF)as well as size classification-fine grain flotation(SC-FGF).The mechanism of its enhanced separation effect was revealed through flotation kinetic fitting,flotation flow foam layer stability,particle size composition,surface morphology,pore structure,and surface chemical property analysis.The results showed that compared with WGF,pre-classification could reduce the collector dosage by 84.09%and the combination of pre-classification and ultrasonic pretreatment could increase the combustible recovery by 17.29%and up to 93.46%.The SC-FGUF process allows the ineffective adsorption of coarse residual carbon to collector during flotation stage to be reduced by pre-classification,and the tightly embedded state of fine CGFS particles is disrupted and surface oxidizing functional group occupancy was reduced by ultrasonic pretreatment,thus carbon and ash is easier to be separated in the flotation process.In addition,some of the residual carbon particles were broken down to smaller sizes in the ultrasonic pretreatment,which led to an increase in the stability of flotation flow foam layer and a decrease in the probability of detachment of residual carbon particles from the bubbles.Therefore,SCFGUF could increase the residual carbon recovery and reduce the flotation collector dosage,which is an innovative method for carbon-ash separation of CGFS with good application prospect.

A Review of the Life Cycle Analysis for Plastic Waste Pyrolysis

Pyrolysis is a rapidly expanding chemical-based recyclable method that complements physical recycling. It avoids improper disposal of post-consumer polymers and mitigates the ecological problems linked to the production of new plastic. Nevertheless, while there is a consensus that pyrolysis might be a crucial technology in the years to come, more discussions are needed to address the challenges related to scaling up, the long-term sustainability of the process, and additional variables essential to the advancement of the green economy. Herein, it emphasizes knowledge gaps and methodological issues in current Life Cycle Assessment (LCA), underlining the need for standardized techniques and updated data to support robust decision-making for adopting pyrolysis technologies in waste management strategies. For this purpose, this study reviews the LCAs of pyrolytic processes, encompassing the complete life cycle, from feedstock collection to end-product distribution, including elements such as energy consumption, greenhouse gas emissions, and waste creation. Hence, we evaluate diverse pyrolysis processes, including slow, rapid, and catalytic pyrolysis, emphasizing their distinct efficiency and environmental footprints. Furthermore, we evaluate the impact of feedstock composition, process parameters, and scale of operation on the overall sustainability of pyrolysis-based plastic waste treatment by integrating results from current literature and identifying essential research needs. Therefore, this paper argues that existing LCA studies need more coherence and accuracy. It follows a thorough evaluation of previous research and suggests new insights into methodologies and restrictions.

Study on pyrolysis and gasification of wood in MSW

In order to develop municipal solid waste（MSW） pyrolysis/gasification and melting technology with low emission and high efficiency, it was planed that all the main components in MSW and some typical kinds of MSW were pyrolyzed/gasified to propose an expert system for raw MSW. In this paper, wood, which was a prevalent component in MSW, was pyrolyzed and gasified in fluidized-bed reactors at different apparent excess air ratios （EARs）, temperatures and fluidizing velocities. For pyrolysis, with tem- perature increasing from 400℃ to 700℃, the yield of pyrolysis char decreased while that of pyrolysis gas increased （in this paper respectively from 28% to 20% and from 10% to 35%）, and when temperature was 500℃, the yield of pyrolysis tar reached the highest, up to 38% in this paper. It was the optimum for gasification when temperature was 600℃ and apparent EAR was 0.4. Under the experimental conditions of this paper, gasification efficiency achieved 73%, lower heat value（LHV） reached 5800 kJ/（Nm^3） and yield of syngas was 2.01 Nm^3/kg. Lower fluidizing velocity was useful to upgrade gasification efficiency and LHV of syngas for wood gasification. Based on the results, the reactive courses and mechanism were analyzed respectively for wood pyrolysis and gasification.

Effect of ash removal on structure and pyrolysis/gasification reactivity of a Chinese bituminous coal

In this study,the effect of ash removal on Shenfu bituminous coal was investigated.The coal was pretreated by hydrofluoric acid(HF)pickling,and the raw/pretreated coal chars were prepared at 900°C in a fixed bed reactor.The structure of coal and char were detected by Fourier transform infrared(FTIR)and Raman spectroscopy.The reactivity was tested in a thermogravimetric analyzer,including coal pyrolysis and char gasification.The reaction kinetics was analyzed through the Coats–Redfern method,master plots,the model-free and model-fitting method.The results show that the HF pickling can remove silicon from coal efficiently,and the macromolecular framework of coal is quite stable according to FTIR.The Raman parameters imply some carbonaceous structure on coal surface changed.For slow pyrolysis of coal,the effect of heating rate is considered.The changes of pyrolysis characteristics and kinetics are insignificant.For char gasification,the reactivity under isothermal and non-isothermal condition are discussed with an emphasis in different residence time of devolatilization process.In kinetic control region(low temperature),the activation energy(Ea)is very close(about 240 kJ/mol)for all chars.With the temperature increases,the reactivity of raw coal char is more easily suffered by diffusion.The random pore model is more suitable for the ash-free coal char,and the char with long residence time has a larger value of structural parameterψand smaller value of pre-exponential factor A.The Ea calculated by model-fitting and model-free method were in good agreement.

Influence of different biomass ash additive on anthracite pyrolysis process and char gasification reactivity

Catalytic coal gasification technology shows prominent advantages in enhancing coal gasification reactivity and is restrained by the cost of catalyst.Two typical biomass ash additions,corn stalk ash(CSA,high K–Na and low Si)and poplar sawdust ash(PSA,high K–Ca and high Si),were employed to study the influence of biomass ash on pyrolysis process and char gasification reactivity of the typical anthracite.Microstructure characteristics of the char samples were examined by X-ray diffraction(XRD).Based on isothermal char-CO2 gasification experiments,the influence of biomass ash on reactivity of anthracite char was determined using thermogravimetric analyzer.Furthermore,structural parameters were correlated with different reactivity parameters to illustrate the crucial factor on the gasification reactivity varied with char reaction stages.The results indicate that both CSA and PSA additives hinder the growth of adjacent basic structural units in a vertical direction of the carbon structure,and then slow down the graphitization process of the anthracite during pyrolysis.The inhibition effect is more prominent with the increasing of biomass ash.In addition,the gasification reactivity of anthracite char is significantly promoted,which could be mainly attributed to the abundant active AAEM(especially K and Na)contents of biomass ash and a lower graphitization degree of mixed chars.Higher K and Na contents illustrate that the CSA has more remarkable promotion effect on char gasification reactivity than PSA,in accordance with the inhibition effect on the order degree of anthracite char.The stacking layer number could reasonably act as a rough indicator for evaluating the gasification reactivity of the char samples.

Kinetic and thermodynamic investigations of CO2 gasification of coal chars prepared via conventional and microwave pyrolysis

This study examined an isothermal CO2 gasification of four chars prepared via two different methods,i.e.,conventional and microwave-assisted pyrolysis,by the approach of thermogravimetric analysis.Physical,chemical,and structural behaviours of chars were examined using ultimate analysis,X-ray diffraction,and scanning electronic microscopy.Kinetic parameters were calculated by applying the shrinking unreacted core(SCM)and random pore(RPM)models.Moreover,char-CO2 gasification was further simulated by using Aspen Plus to investigate thermodynamic performances in terms of syngas composition and cold gas efficiency(CGE).The microwave-induced char has the largest C/H mass ratio and most ordered carbon structure,but the smallest gasification reactivity.Kinetic analysis indicates that the RPM is better for describing both gasification conversion and reaction rates of the studied chars,and the activation energies and pre-exponential factors varied in the range of 78.45–194.72 kJ/mol and 3.15–102,231.99 s−1,respectively.In addition,a compensation effect was noted during gasification.Finally,the microwave-derived char exhibits better thermodynamic performances than the conventional chars,with the highest CGE and CO molar concentration of 1.30%and 86.18%,respectively.Increasing the pyrolysis temperature,gasification temperature,and CO2-to-carbon molar ratio improved the CGE.

Influence of carbon coating prepared by microwave pyrolysis on properties of LiNi_(1/3) Mn_(1/3) Co_(1/3) O_2

A novel synthesis method of carbon-coated LiNil/3Mnl/3COl/302 cathode material for lithium-ion battery was reported. The carbon coating was produced from a precursor, glucose, by microwave-pyrolysis method. The prepared powders were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, X-ray fluorescence （XRF） and charge/discharge tests. XRD results indicate that the carbon coating does not change the phase structure of LiNil/3Mnl/3C01/302 material. SEM results show that the surface of spherical carbon-coated material becomes rough. Electrochemical performance results show that the carbon coating can improve the cycling performance of LiNii/3Mnl/3C01/302. The specific discharge capacity retention of the carbon-coated LiNi1/3Mnt/3Col/30z reached 85.0%-96.0% at the 50th cycle at 0.2C rate, and the specific discharge capacity retention is improved at a high rate.

Offgas Analysis and Pyrolysis Mechanism of Activated Carbon from Bamboo Sawdust by Chemical Activation With KOH

Bamboo sawdust was used as the precursor for the multipurpose use of waste. Offgases released during the activation process of bamboo by KOH were investigated quantitatively and qualitatively by a gas analyzer. TG/DTG curves during the pyrolysis process with different impregnation weight ratios （KOH to bamboo） were obtained by a thermogravimetric analyzer. Pyrolysis mechanism of bamboo was proposed. The results showed that the offgases were composed of CO, NO, SO2 and hydrocarbon with the concentration of 1 372, 37, 86, 215 mg/L, respectively. Thermogravimetric analysis indicated that the pyrolytic process mainly experienced two steps. The first was the low temperature activation step （lower than 300 ℃）, which was the pre-activation and induction period. The second was the high temperature activation step（higher than 550 ℃）, which was a radial activation followed by pore production. The second process was the key to control the pore distribution of the final product.

N/S co-doped 3D carbon framework prepared by a facile morphology-controlled solid-state pyrolysis method for oxygen reduction reaction in both acidic and alkaline media

Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.

DFT Thermodynamic Research of the Pyrolysis Mechanism of the Carbon Matrix PrecursorTol uene for Carbon Material

Based on the experiments, the standard enthalpy△H■of the possible pyrolysis reactions of the carbon matrix precursor toluene was investigated by means of DFT method UB3LYP/ 3-21G *(based on semi-empirical method UAM1 and ab initio method UHF/3-21G*). The com- putation results with UB3LYP/3-21G* coincide with the experimental values well. Then, the mechanism for all types of the pyrolysis reactions of toluene was studied by UB3LYP/3-21G * The geometries of the reactant and the product radicals were optimized, meanwhile, the standard thermodynamic parameters of the pyrolysis reaction at different temperatures (298, 773, 843, 963 and 1 073 K) were calculated. The thermodynamic computation result shows that when the pyrolysis temperature of toluene is lower than 963 K, the reaction path supported by thermody- namics is that the C-H bond of the methyl on the benzene ring breaks and bitoluene form, while the temperature increases (about 1 073 K), the thermodynamic calculation result turns to support the reaction path producing phenyl radicals and methyl radicals. This mechanism is in accord with the experiments.

Sucrose pyrolysis assembling carbon nanotubes on graphite felt using for vanadium redox flow battery positive electrode

In the present paper, multi-walled carbon nanotubes（MWCNTs） are successfully assembled on graphite felt（GF） using sucrose pyrolysis method for the first time. The in situ formed pyrolytic carbon is chosen as the binder because it is essentially carbon materials as well as CNTs and GF which has a natural tendency to achieve high bonding strength and low contact resistance. The MWCNTs/GF electrode is demonstrated to increase surface area, reduce polarization, lower charge transfer resistance and improve energy conversion efficiency comparing with GF. This excellent electrochemical performance is mainly ascribed to the high electro-catalytic activity of MWCNTs and increasing surface area.

Influence of coal properties on coal conversion processes-coal carbonization,carbon fiber production,gasification and liquefaction technologies:a review

Coal due to its relatively large quantities and wide distribution worldwide has generated renewed interest in research and development with the aim of establishing coal conversion technologies that are technically reliable,envi-ronmentally and economically feasible.It has proved to be a prominent energy source in emerging markets with increasing energy demand by accounting for the largest increase in the demand of energy amongst all other energy sources.Fur-thermore,with its higher mesophase content,coal tar is an appropriate raw material for precursors in the production of carbon fiber.However,whenever a material is put to use,it is important to be able to associate its properties to the behavioral characteristics during a conversion process so as to have a basis for opting for the material in a given process or adjusting the operating conditions in order to optimize the material utilization.Therefore,as with any other material,it is important to be able to relate the properties of coal to its utilization.A review was carried out on the influence of coal properties on four main utilization technologies:gasification,carbonization,liquefaction and carbon fibre production.Among several properties rank,type,mineral matter content,distribution of trace elements,structural composition and pore structure were found to be most influential on the behavior of coal during conversion processes.

CO2-hierarchical activated carbon prepared from coal gasification residue: Adsorption equilibrium, isotherm, kinetic and thermodynamic studies for methylene blue removal

Mineral matter in a residue(RC G)from coal gasification(CG)was removed by two-stage acid leaching.Hierarchical activated carbon(HAC)was prepared by activating RC Gwith CO2.The performance of HAC on removing methylene blue(MB)from an aqueous solution was investigated.HAC was characterized by N2 adsorption–desorption isotherm,Fourier transform infrared spectroscopy,and scanning electron microscopy.The results show that HAC exhibits hierarchical pore structure with high specific surface area(862.76 m2·g-1)and total pore volume(0.684 cm3·g-1),and abundant organic functional groups.The adsorption equilibrium data of MB on HAC are best fitted to the Redlich-Peterson.The kinetic data show that the pseudo-first-order model is more suitable at low MB concentration,while the advantages of the pseudo-second-orderand the Elovich models are more obvious as the concentration increases.According to the thermodynamic parameters,the HAC-MB adsorption process is spontaneous and endothermic.

Characterization of Carbon Deposits Formed During Plasma Pyrolysis of Xinjiang Candle Coal

Carbon deposits were formed on the reactor wall during plasma pyrolysis of the Xinjiang candle coal in our V-style plasma pyrolysis pilot-plant. The carbon deposits were studied using a scanning electronic microscope （SEM） and the X-ray diffraction （XRD） method. It was found that carbon deposits located at different parts in the reactor exhibited different microscopic patterns. The formation mechanism of the carbon deposits was deduced. The downward increase in the graphitization degree of the carbon deposits was found and interpreted.

Effect of supercritical water on the stability and activity of alkaline carbonate catalysts in coal gasification

The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 on coal are more stable than that of K2CO3, but the stability of Na2CO3 is strongly reduced as the cluster gets larger. In supercritical water system, the dispersion and stability of Na2CO3 catalyst on coal support is strongly improved. During coal gasification process, Na2CO3 transforms with supercritical water into NaOH and NaHCO3, which is beneficial for hydrogen production. The transformation process has been studied via thermodynamics and kinetics ways. The selectively catalytic mechanism of NaOH and the intermediate form of sodium-based catalyst in water-gas shift reaction for higher hydrogen production has also been investigated. Furthermore, NaOH can transform back to Na2CO3 after catalyzing the water-gas shift reaction. Thus, the cooperative effects between supercritical water and Na2CO3 catalyst form a benignant circle which greatly enhances the reaction rate of coal gasification and promotes the production of hydrogen.

Preparation of CaO-containing carbon pellets from coking coal and calcium oxide:Effects of temperature,pore distribution and carbon structure on compressive strength in pyrolysis furnace

CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350-750℃).The results showed that as the roasting temperature increased,the compressive strength also increased and furthermore,structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures,thus forming high-ordered CC.Notably,the CCCP preheated at 750℃exhibited the highest compressive strength.A positive relationship between the compressive strength and pore-size homogeneity was established.A linear relationship between the com-pressive strength of the CCCP and the average stack height of CC was observed.Additionally,a four-stage caking mechanism was developed.

Catalytic effect of alkali carbonates on CO_2 gasification of Pingshuo coal

Na2CO3, Li2CO3, and K2CO3 were used as additives to Pingshuo （PS） coal that was subsequently gasified under a CO2 stream. The catalytic gasification of coal samples by CO2 in the presence single or mixed alkali carbonates was investigated by thermogravimetric analysis. The experimental results indicate that the catalytic effect of Li2CO3 is significantly larger than that of Na2CO3 or K2CO3. The catalytic effect of the mixed, bi-metal carbonate containing Li2C03 and Na2C03, or Li2CO3, and K2C03, is related to the compo- sition of the catalyst and the proportion of the two components. The bi-metal carbonates having a mole ratio of 9：1 （lri：x） has the largest catalytic effect for PS coal gasification. A synergistic effect between Li and K, or Na, carbonate appears at temperatures greater than 1300 K. An un-reacted shrinking core model is suitable for kinetic analysis of catalytic gasification of coal samples in the presence of alkali carbonates. It is inappropriate, however, to evaluate the catalytic effect only by the activation energy obtained from the kinetic calculations.