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.

Microwave irradiation-induced alterations in physicochemical properties and methane adsorption capability of coals:An experimental study using carbon molecular sieve

In order to comprehend the applicability of microwave irradiation for recovering coalbed methane,it is necessary to evaluate the microwave irradiation-induced alterations in coals with varying levels of metamorphism.In this work,the carbon molecular sieve combined with KMnO_(4)oxidation was selected to fabricate carbon molecular sieve with diverse oxidation degrees,which can serve as model substances toward coals.Afterwards,the microwave irradiation dependences of pores,functional groups,and highpressure methane adsorption characteristics of model substances were studied.The results indicated that microwave irradiation causes rearrangement of oxygen-containing functional groups,which could block the micropores with a size of 0.40-0.60 nm in carbon molecular sieve;meanwhile,naphthalene and phenanthrene generated by macro-molecular structure pyrolysis due to microwave irradiation could block the micropores with a size of 0.70-0.90 nm.These alterations in micropore structure weaken the saturated methane adsorption capacity of oxidized carbon molecular sieve by 2.91%-23.28%,suggesting that microwave irradiation could promote methane desorption.Moreover,the increased mesopores found for oxidized carbon molecular sieve after microwave irradiation could benefit CH4 diffusion.In summary,the oxidized carbon molecular sieve can act as model substances toward coals with different ranks.Additionally,microwave irradiation is a promising technology to enhance coalbed methane recovery.

Ash removal from inferior coal via ammonium fluoride roasting and simultaneous yield of white carbon black

The quality upgrading and deashing of inferior coal by chemical method still faces great challenges.The dangers of strong acid,strong alkali,waste water and exhaust gas as well as high cost limit its industrial production.This paper systematically investigates the ash reduction and desilicification of two typical inferior coal utilizing ammonium fluoride roasting method.Under the optimal conditions,for fat coal and gas coal,the deashing rates are 69.02%and 54.13%,and the desilicification rates are 92.64%and 90.27%,respectively.The molar dosage of ammonium fluoride remains consistent for both coals;however,the gas coal,characterized by a lower ash and silica content(less than half that of the fat coal),achieves optimum deashing effect at a reduced time and temperature.The majority of silicon in coal transforms into gaseous ammonium fluorosilicate,subsequently preparing nanoscale amorphous silica with a purity of 99.90%through ammonia precipitation.Most of the fluorine in deashed coal are assigned in inorganic minerals,suggesting the possibility of further fluorine and ash removal via flotation.This research provides a green and facile route to deash inferior coal and produce nano-scale white carbon black simultaneously.

A new preparation process of coal-based magnetically activated carbon

Fe/C-based magnetically activated carbon(MAC) was obtained by carbonizing and activating its precursor, that was prepared by co-precipitation of anthracite coal impregnated in ferric chloride solution. The effect of the concentrations of FeCl3 and pH of solution on BET surface area, pore volume and magnetic properties of the MAC was studied by BET N2 adsorption and VSM method. The results indicated that the magnetization of MAC gradually increases with increasing concentration of FeCl3 and pH value of solution, and BET surface area was inclined to fluctuation. The largest BET surface area and magnetization of MAC were 1327.5 m2/g and 35.56 emu/g, respectively. The form of magnetic matter in the magnetically activated carbon was mainly Fe3C by X-ray powder diffraction(XRD) and magnetic attraction test.

Preparation of pitch precursor with excellent spinnability for general-purpose carbon fibre using coal tar pitch as raw material

Tetrahydrofuran(THF) extract of coal tar pitch(CTP) was used instead of blending CTP with pretreated pyrolysis fuel oil to prepare an isotropic pitch precursor with excellent spinnability for general-purpose carbon fibre through bromination-dehydrobromination. The feasibility and effectiveness of synthesising an isotropic pitch precursor derived from THF-soluble(CTP-THFs) is demonstrated in this study.The results show that CTP-THFs contains more light components than CTP;CTP-THFs and CTP monomer proportions were 62.52% and 45.32%, respectively. However, based on comparisons of CTP-THFsBr0 and CTPBr0 characterisations, CTP-THFs exhibits better polycondensation than CTP. Bromination-dehydrobro mination promotes polycondensation of pitch precursors, leading to greater carbon aromaticity in CTP-THFsBr5, CTP-THFsBr10, and CTP-THFsBr15 than that in CTP-THFsBr0 and CTPBr0. CTP-THFsBr5 and CTP-THFsBr10 have excellent spinnability even with softening points as high as 230 ℃. The pericondensed carbon and carbon aromaticity of CTP-THFsBr5 and CTP-THFsBr10 are high owing to the higher degree of polycondensation;however, they still possess a more linear molecular structure. The as-prepared carbon fibre exhibits homogeneity and uniformity, and the mechanical performance is comparable with that of commercial general-purpose carbon fibre products.

Catalytic graphitization of Mo-B-doped polyacrylonitrile(PAN)-based carbon fibers

A novel carbon fiber pretreatment was proposed.Polyacrylonitrile(PAN)-based carbon fibers were first anodized in H3PO4 electrolyte to achieve an active surface,and then coated with Mo-B catalysts by immersed the carbon fibers in a uniformly dispersed Mo-B sol.The as-treated carbon fibers were then graphitized at 2 400 ℃ for 2 h.The structural changes were characterized by X-ray diffractometry(XRD),Raman spectroscopy,scanning electron microscopy(SEM) and high-resolution transmission electronic microscopy(HRTEM).The results show that much better graphitization can be achieved in the presence of Mo-B,with an interlayer spacing(d002) of 0.335 8 nm and a crystalline size(Lc) of 28 nm.

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.

Bioleaching of vanadium from stone coal vanadium ore by Bacillus mucilaginosus:Influencing factors and mechanism

Vanadium and its derivatives are used in various industries,including steel,metallurgy,pharmaceuticals,and aerospace engineering.Although China has massive reserves of stone coal resources,these resources have low grades.Therefore,the effective extraction and recovery of metallic vanadium from stone coal is an important way to realize the efficient resource utilization of stone coal vanadium ore.Herein,Bacillus mucilaginosus was selected as the leaching strain.The vanadium leaching rate reached 35.5%after 20 d of bioleaching under optimal operating conditions.The cumulative vanadium leaching rate in the contact group reached 35.5%,which was higher than that in the noncontact group(9.3%).The metabolites of B.mucilaginosus,such as oxalic,tartaric,citric,and malic acids,dominated in bioleaching,accounting for 73.8%of the vanadium leaching rate.Interestingly,during leaching,the presence of stone coal stimulated the expression of carbonic anhydrase in bacterial cells,and enzyme activity increased by 1.335-1.905 U.Enzyme activity positively promoted the production of metabolite organic acids,and total organic acid content increased by 39.31 mg·L^(-1),resulting in a reduction of 2.51 in the pH of the leaching system with stone coal.This effect favored the leaching of vanadium from stone coal.Atomic force microscopy illustrated that bacterial leaching exacerbated corrosion on the surface of stone coal beyond 10 nm.Our study provides a clear and promising strategy for exploring the bioleaching mechanism from the perspective of microbial enzyme activity and metabolites.

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.

Recovery of vanadium and carbon from low-grade stone coal by flotation

Flotation technology of high-carbon stone coal bearing vanadium was investigated based on mineralogical study. Carbon and vanadium flotation circuits were included in the flotation process for carbon and vanadium mineral concentrates. Carbon and vanadium minerals were efficiently separated via regrinding process in the carbon flotation circuit. The results show that the grade and recovery of V2O5 in flotation concentrate are 1.32% and 88.38%, respectively, and the tailings yield is 38.36%. Meanwhile, the grade and recovery of the carbon mineral are 30.08% and 75.10%, respectively, which may be utilized as the fossil fuels directly. The leaching rates of the flotation products are as high as 85%. The results demonstrate that there is no direct adverse effect of flotation process on vanadium leaching. This technology could potentially reduce cost and increase the treatment capacity of vanadium extraction and provide reference to stone coal flotation technology.

Preparation of magnetically separable mesoporous activated carbons from brown coal with Fe3O4

Magnetically separable mesoporous activated carbon was prepared from brown coal in the presence of Fe3O4 as a bi-functional additive.Magnetic activated carbon(MAC)was characterized by lowtemperature nitrogen adsorption,scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS)and vibrating sample magnetometry(VSM).The evolution behaviors and transition mechanism of Fe3O4 during the preparation of MAC were investigated.The results show that prepared MAC with 6 wt%Fe3O4 addition having a specific surface area and mesopore ratio of 370 m^2·g^-1 and 55.7%,which meet the requirements of adsorption application and magnetic recovery.Highly dispersed iron-containing aggregates with the size of 0.1 lm in the MAC were observed.During the preparation of MAC,Fe3O4 could enhance the escape of volatiles during the carbonization.Fe3O4 could also accelerate burning off the carbon wall during activation,which leads to enlarging micropore size,then resulting in the generation of mesopore and macropore.As a result,a part of Fe3O4 converted into FeO,FeOOH,a-Fe,c-Fe,Fe2SiO4 and compound of Aluminum-iron-silicon.The prepared activated carbon,which was magnetized by both of residual Fe3O4,reduced a-Fe and c-Fe,can be easily separated from the original solution by external magnetic field.

Conversion of Malaysian low-rank coal to mesoporous activated carbon:Structure characterization and adsorption properties

Malaysian Selantik low-rank coal(SC)was used as a precursor to prepare a form of mesoporous activated carbon(SC-AC)with greater surface area(SA)via a microwave induced KOH-activation method.The characteristics of the SC and SC-AC were evaluated by the iodine number,ash content,bulk density,and moisture content The structure and surface characterization was carried out using pore structure analysis(BET),scanning electron microscopy with energy dispersive X-ray spectroscopy(SEM-EDX),X-ray diffraction(XRD),Fourier Transform Infrared(FTIR),elemental analysis(CHNS),thermogravimetric analysis(TGA),and determination of the point of zero charge(pH(PZC)).These results signify a mesoporous structure of SC-AC with an increase of ca.1160 times(BET SA=1094.3 m^2·g^-1)as compared with raw SC without activation(BET SA=1.23 m^2·g^-1).The adsorptive properties of the SC-AC with methylene blue(MB)was carried out at variable adsorbent dose(0.2-1.6 g·L^-1),solution pH(2-12),initial MB concentrations(25-400 mg·L^-1),and contact time(0-290 min)using batch mode operation.The kinetic profiles follow pseudo-second order kinetics and the equilibrium uptake of MB conforms to the Langmuir model with a maximum monolayer adsorption capacity of 491.7 mg g^-1 at 303 K.Thermodynamic functions revealed a spontaneous endothermic adsorption process.The mechanism of adsorption included mainly electrostatic attractions,hydrogen bonding interaction,andπ-πstacking interaction.This work shows that Malaysian Selantik low-rank coal is a promising precursor for the production of low-cost and efficient mesoporous activated carbon with substantive surface area.

Quantitative Analysis of Carbon Content in Bituminous Coal by Laser-Induced Breakdown Spectroscopy Using UV Laser Radiation

The carbon content of bituminous coal samples was analyzed by laser-induced breakdown spectroscopy. The 266 nm laser radiation was utilized for laser ablation and plasma generation in air. The partial least square method and the dominant factor bused PLS method were used to improve the measurement accuracy of the carbon content of coal. The results showed that the PLS model could achieve good measurement accuracy, and the dominant factor based PLS model could further improve the measurement accuracy. The coefficient of determination and the root-mean-square error of prediction of the PLS model were 0.97 and 2.19%, respectively; and those values for the dominant factor based PLS model were 0.99 and 1.51%, respectively. The results demonstrated that the 266 nm wavelength could accurately measure the carbon content of bituminous coal.

A Carbon Isotopic Stratigraphic Pattern of the Late Palaeozoic Coals in the North China Platform and Its Palaeoclimatic Implications

This paper gives the stable carbon isotopic data in coals from the Late Namurian to Kazanian stages in the Serteng Mt., Xishan and Huainan coalfields of the North China Platform. Its stratigraphic pattern shows that several isotopic shifts are apparent, and the large δ13C negative shifts (approximately 2.5 to 3.0 %%) occurred during the Stephanian, Artinskian and Kazanian are observed in three Permo-Carboniferous coalfields. Those negative shifts are neither related to the coal rank and coal macerals, nor caused by the variety of peat-forming plants. The general decrease in the δ13C values of the Stephanian, Artinskian and Kazanian coals is consistent with an overall decrease in the δ13C values of ambient atmospheric CO2 and/or a relative increase in atmospheric Pco2 during the coal-forming periods. Therefore the authors postulate that the oxidation of peat, and the δ13C-depleted CO2 flux into the atmosphere during the above stages may have contributed to coeval palaeoclimatic warming by way of the greenhouse effect.

The view of technological innovation in coal industry under the vision of carbon neutralization

This paper analyzed the current situation and development trends of energy consumption and carbon emissions,and the current situation and development trend of coal consumption in China.In the context of recently established carbon peak and carbon neutralization targets,this paper put forward the main problems associated with the green and low-carbon development and utilization of coal.Five key technological innovation directions in mining were proposed,including green coal development,intelligent and efficient mining,low-carbon utilization and conversion of coal,energy conservation and emission reduction,carbon capture,utilization and storage(CCUS).Focusing on the above technological innovation directions,it is suggested to carry out three basic theories,including the theory of green efficient intelligent mining,clean and low-carbon utilization and transformation of coal,and CCUS.Meanwhile,it is proposed to develop 12 key technologies,including green coal mining and ecological environment protection,efficient coal mining and intelligent mine construction,key technologies and equipment for efficient coal processing,underground coal gasification and mining,ultra-high parameter and ultra-supercritical power generation technology,intelligent and flexible coal-fired power generation technology,new power cycle coal-fired power generation technology,the development of coal-based special fuels,coal-based bulk and specialty chemicals,energy conservation and consumption reduction,large-scale and low-cost carbon capture,CO_(2) utilization and storage.Finally,necessary measures from the governmental perspective were also proposed.

SnO_2-based solid solutions for CH_4 deep oxidation: Quantifying the lattice capacity of SnO_2 using an X-ray diffraction extrapolation method

A series of SnO2‐based catalysts modified by Mn, Zr, Ti and Pb oxides with a Sn/M （M=Mn, Zr, Ti and Pb） molar ratio of 9/1 were prepared by a co‐precipitation method and used for CH4 and CO oxidation. The Mn3＋, Zr4＋, Ti4＋and Pb4＋cations are incorporated into the lattice of tetragonal rutile SnO2 to form a solid solution structure. As a consequence, the surface area and thermal stability of the catalysts are improved. Moreover, the oxygen species of the modified catalysts become easier to be reduced. Therefore, the oxidation activity over the catalysts was improved, except for the one modified by Pb oxide. Manganese oxide demonstrates the best promotional effects for SnO2. Using an X‐ray diffraction extrapolation method, the lattice capacity of SnO2 for Mn2O3 was 0.135 g Mn2O3/g SnO2, which indicates that to form stable solid solution, only 21%Sn4＋cations in the lattice can be maximally replaced by Mn3＋. If the amount of Mn3＋cations is over the capacity, Mn2O3 will be formed, which is not favorable for the activity of the catalysts. The Sn rich samples with only Sn‐Mn solid solution phase show higher activity than the ones with excess Mn2O3 species.

Preparation of mesoporous activated carbons from coal liquefaction residue for methane decomposition

Mesoporous activated carbons were prepared from direct coal liquefaction residue （CLR） by KOH activation method, and the experiments were carried out to investigate the effects of KOH/CLR ratio, solvent for mixing the CLR and KOH, and carbonization procedure on the resultant carbon texture and catalytic activity for catalytic methane decomposition （CMD）. The results showed that optimal KOH/CLR ratio of 2 ： 1; solvent with higher solubility to KOH or the CLR, and an appropriate carbonization procedure are conductive to improving the carbon pore structure and catalytic activity for CMD. The resultant mesoporous carbons show higher and more stable activity than microporous carbons. Additionally, the relationship between the carbon textural properties and the catalytic activity for CMD was also discussed.

Effects of coal rank, Fe_3O_4 amounts and activation temperature on the preparation and characteristics of magnetic activated carbon

Coal-based Magnetic Activated Carbons （CMAC＇s） were prepared from three representative coal samples of various ranks： Baorigele lignite from Inner Mongolia; Datong bitumite from Shanxi province; and Taixi anthracite from Ningxia Hui Auto- nomous Region. Fe3O4 was used as a magnetic additive. A nitrogen-adsorption analyzer was used to determine the specific surface area and pore structure of the resulting activated carbons. The adsorption capacity was assessed by the adsorption of iodine and methylene blue. X-ray diffraction was used to measure the evolution behavior of Fe304 during the preparation process. Magnetic properties were characterized with a vibrating-sample magnetometer. The effect of the activation temperature on the performance of CMAC＇s was also studied. The results show that, compared to Baorigele lignite and Taixi anthracite, the Datong bitumite is more appropriate for the preparation of CMAC＇s with a high specific surface area, an advanced pore structure and suitable magnetic properties. Fe304 can effectively enhance the magnetic properties and control the pore structure by increasing the ratio of meso- pores. An addition of 6.0% Fe304 and an activation temperature of 880 ℃ produced a CMAC having a specific surface area, an iodine adsorption, a methylene blue adsorption and a specific saturation magnetization of 1152.0 m2/g, 1216.7 mg/g, 229.5 mg/g and 4.623 emu/g, respectively. The coal used to prepare this specimen was Datong bitumite.

Earth-abundant coal-derived carbon nanotube/carbon composites as efficient bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries and regenerative fuel cells.Here we report facile synthesis of three-dimensional(3 D)carbon nanotube(CNT)/carbon composites using earth-abundant coal as the carbon source,hydrogen reductant and heteroatom dopant to grow CNTs.The prepared composite featuring 3 D structural merits and multiple active sites can efficiently catalyze both ORR and OER,affording high activity,fast kinetics,and long-term stability.With the additional incorporation of manganese,the developed catalyst afforded a potential difference of 0.80 V between ORR at the half wave potential and OER at a current density of 10 mA cm^(-2).The optimized sample has presented excellent OER performance within a constructed solar-powered water splitting system with continuously generating oxygen bubbles at anode.Notably,it can be further used as a durable air-electrode catalyst in constructed Zn-air battery,delivering an initial discharge/charge voltage gap of 0.73 V,a remained voltaic efficiency of 61.2%after 160 cycles and capability to power LED light for at least 80 h.This study provides an efficient approach for converting traditional energy resource i.e.coal to value-added alternative oxygen electrocatalysts in renewable energy conversion systems.

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.