Features of rare earth elements geochemistry in coals of Central Kazakhstan

This research presents the results of a comprehensive study of mineralogical and geochemical features of REE distribution in coals of Central Kazakhstan deposits—Karaganda coal basin and Shubarkol deposit,which have large hard coal reserves and are industrially important for the coal industry of Kazakhstan;the research is based on 205 samples of clayey interlayers and coal seams.It shows basic patterns of distribution and features of concentration for impurity elements,gives an estimate of the impurity elements concentration,including REE,defines conditions and factors of their accumulation,and studies features of their forms in coal and coal-bearing rocks,which allows estimating the mechanisms of their migration and conditions of accumulation.According to the results of geochemical indicators,the article establishes the factors of REE dislocation,reveals the composition of margin rocks that have influenced REE concentration in coal seams,and the presented latest data on mineralogy allowed to establish the ways of their transportation to the paleobasin during the synand epigenetic periods of formation of the coal deposits of Central Kazakhstan being researched.It was found that the coals are insignificantly enriched with heavy lanthanides from Ho to Lu.The distribution curves of UCC normalized REE values in the coals are similar and coincide,but they are less than the average value for world coal,and amount to only one-third of the UCC.It was found that the highest concentrations of all REE are characteristic of clayey interlayers and oxidized coals.The La/Yb ratio in this case increases upwards along the section,indicating mainly clastogenic mechanism of REE delivery to the coals.In coal and clay samples,the predominant mineral form of REE is light lanthanide phosphates.Identified particles of REE from minerals and their composition peculiarities suppose autigene nature of their formation.The formation of the bulk of autigene minerals occurred during the maturation of brown coals and their transformation into hard ones.

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.

Effects of coals microscale structural features on their mechanical properties,propensity to crushing and fine dust formation

The work is dedicated to revealing the structural features of coals with different ranks,such as anthracites,metaanthracite and graphite,that determine their ability to crush and form fine dust.For this purpose,a combination of various nanoin-dentation techniques and Raman spectroscopy was used.The mechanical behavior of the selected coals was investigated by cyclic nanoindentation with increasing peak load and quasi-static loading.The alteration of the mechanical properties was studied by analysis of elastic moduli and damage indices Rw.Three groups of coals were identified based on their propensity to crushing during cyclic nanoindentation.Coals assigned to the first and second groups are characterized by local destruction in the contact zone with the indenter and the formation of a core of crushed material.Coals assigned to the third group are characterized by bulk destruction(outside the zone of contact with the indenter).In general,the ability of coals to fracture under mechanical loading decreases in the series of metamorphism due to microscale compaction of vitrinite matter.In the series of anthracite,metaanthracite and graphite,it is established that the coal matter compaction takes place for the anthracite and metaanthracite,whereas graphite reveals rather different behavior due to abrupt change of its structure.The ratios between the amorphous and crystalline phases of carbon(S)were determined by deconvolution of coals Raman spectra.The propensity of coals to crushing(a damage index Rw)increases with growth of the proportion of amorphous carbon in the coal matter.For the considered coals and metaanthracite,it is established that the proneness to destruction outside the contact zone with the indenter is determined by the ratio of amorphous and crystalline carbon of 1 and higher.When S parameter is lower than 1,the coals are being crushed only in the zone of contact with the indenter.

Experimental investigations on effects of gas pressure on mechanical behaviors and failure characteristic of coals

The mechanical behavior of coal is the key factor affecting underground coal mining and coalbed methane extraction.In this study,triaxial compression and seepage tests were carried out on coal at different gas pressures.The mechanical properties and failure process of coal were studied,as well as the acoustic emission(AE)and strain energy.The influence of gas pressure on the mechanical parameters of this coal was analyzed.Based on the conventional energy calculation formula,the pore pressure was introduced through the effective stress formula,and each energy component of coal containing gas was refined innovatively.The contribution of gas pressure to the total energy input and dissipation during loading was quantitatively described.Finally,the influence of gas pressure on coal strength was theo-retically analyzed from the perspectives of MohreCoulomb criterion and fracture mechanics.The results show that the total absorbed energy comprises the absorbed energy in the axial pressure direction(positive)and in the confining pressure direction(negative),as well as that induced by the pore pressure(initially negative and then positive).The absorbed energy in the axial pressure direction accounts for the main proportion of the total energy absorbed by coal.The quiet period of AE in the initial stage shortens,and AE activity increases during the pre-peak stage under high gas pressure.The fractal characteristics of AE in three stages are studied using the correlation dimension.The AE process has different forms of self-similarity in various deformation stages.

Insight into the key kinetic steps in the pyrolysis of coking and non-coking coals,characterization of the pyrolysis products

The chemical composition,structural and plastometric properties of different-ranked coals from Mongolia deposits were studied.The non-isothermal iso-conversion Ozawa-Flynn-Wall and Friedman model-free methods were used to assess kinetic parameters and to differentiate decomposition steps.Key peculiarities of the pyrolysis kinetics of brown and bituminous coals were revealed and discussed in terms of the composition and plastometric properties.Brown coal was shown to undergo three decomposition steps with ever increasing activation energy as temperature increased because of the decomposition of thermally more and more stable molecular fragments.The pyrolysis of bituminous coals occurred in four steps,the activation energy having extreme mode of temperature dependence.An important new finding was that the temperature range of the second,major pyrolysis step well corresponded to that between the softening and re-solidification temperatures according to Gieseler plastometry.The yield and composition of the pyrolysis products obtained under isothermal conditions were also characterized depending on coal rank and temperature,and the ways for qualified utilizations were offered.

Effect of Bio-Based Organic‒Inorganic Hybrid Hydrogels on Fire Prevention of Spontaneous Combustion of Coals

To solve the fire accidents caused by coal combustion,this work prepared four hybrid hydrogel materials using bio-based polymers,flame retardants,and inorganic materials.Compared to pure water and 3.5 wt%MgCl_(2)solution,the as-prepared hydrogel presents good fire prevention performance.In addition,it is found that CO and CO_(2)are not produced by coal when the pyrolysis temperature is lower than 200℃.During low-temperature pyrolysis,CO is more likely to be produced than CO_(2),indicating inadequate pyrolysis behavior.At the same time,the addition of fire-preventing hydrogel can not only decrease the maximum CO_(2)concentration before the critical temperature but also prolong the corresponding time.In addition,based on the cone calorimeter test,the inhibition effects of pure water,magnesium chloride solution,and four hybrid hydrogels on heat release behavior are evaluated.It is demonstrated that different dosages of different hydrogels affected the fire prevention effect.Phosphorous-modified cellulose/silica and carrageenan/DMMP/vermiculite composite hydrogels have the weakest fire prevention effect at 20 g,which is weaker than that of water.However,the fire prevention effect of carrageenan/DMMP/vermiculite composite hydrogels exceeded that of water at 40 and 60 g.Additionally,the fire prevention effect of the sodium alginate/sepiolite/ammonium polyphosphate composite hydrogel is most significant in common tests,attributed to the intumescent flame retardant system.

Feasibility studies on cleaning of high sulfur coals by using ionic liquids

Coal has been used as an energy resource around the world, primarily for the generation of electricity. The cleaning of coal by removing its unwanted sulfur and mineral matter components is utmost essential before their gainful utilizations. The ionic liquids （ILs） are considered as non-toxic solvents for using in different industrial processes. The effect of two ILs namely, 1-n-butyl, 3-methylimidazolium tetrafluoro borate （ILl） and 1-n-butyl, 3-methylimidazolium chloride （IL2） in oxidative de-sulfurization and de-ashing of two industrially important high sulfur coal samples from Meghalaya （India） is discussed in this paper. The maximum removal of total sulfur, pyritic sulfur, sulfate sulfur and organic sulfur are observed to be 37.36 %, 62.50 %, 83.33 % and 31.63 % respectively during this oxidative process. The quantitative diffuse reflectance Fourier transform-infrared spectroscopy analysis supports the formation of sulfoxides （S--O） and sulfones （-SO2） and their subsequent removal during the oxidation of the coals in presence of ILs. The X-ray fluorescence combined with near edge X-ray absorption fine structure and scanning electron microscopic studies reveal the removal of mineral matters （ash yields） from the coal samples. The thermogravimetric analysis of the raw and clean coals indicates their high combustion efficiencies and suitability for using in thermal plants. The method is partially green and the ILs could be recovered and reused in the process.

Micro-structural evolution and their effects on physical properties in different types of tectonically deformed coals

The macromolecular structure of tectonically deformed coals(TDC)may be determined by the deformation mechanisms of coal.Alterations of the macromolecular structure change the pore structure of TDC and thereby impact physical properties such as porosity and permeability.This study focuses on structure and properties of TDC from the Huaibei and Huainan coal mining areas of southern North China.Relationships between the macromolecular structure and the pore structure of TDC were analyzed using techniques such as X-ray diffraction,high-resolution transmission electron microcopy,and the low-temperature nitrogen adsorption.The results indicated that the directional stress condition can cause the arrangement of basic structural units(BSU)more serious and closer.And,the orientation is stronger in ductile deformed coal than in brittle deformed coal.Tectonic deformation directly influences the macromolecular structure of coal and consequently results in dynamic metamorphism.Because the size of BSU in brittle deformed coal increases more slowly than in ductile deformed coal,frictional heating and stress-chemistry of shearing areas might play a more important role,locally altering coal structure under stress,in brittle deformed coal.Strain energy is more significant in increasing the ductile deformation of coal.Furthermore,mesopores account for larger percentage of the nano-scale pore volume in brittle deformed coals,while mesopores volume in ductile deformed coal diminishes rapidly along with an increase in the proportion of micropores and sub-micropores.This research also approved that the deformations of macromolecular structures change nano-scale pore structures,which are very important for gas adsorption and pervasion space for gas.Therefore,the exploration and development potential of coal bed methane is promising for reservoirs that are subjected to a certain degree of brittle deformation(such as schistose structure coal,mortar structure coal and cataclastic structure coal).It also holds promise for TDC resulting from wrinkle structure coal of low ductile deformation and later superimposed by brittle deformation.Other kinds of TDC suffering from strong brittle-ductile and ductile deformation,such as scale structure coal and mylonitic structure coal,are difficult problems to resolve.

Mode of occurrence of arsenic in high-As coals from endemic arsenosis areas in southwestern Guizhou Province, China

The use of high As-bearing coals has caused more than 3,000 cases of arsenosis patients in southwest Guizhou Province, China. The mode of occurrence of arsenic in coal is an important key role in understanding its behavior during usage and damage pathway to human health. Coal samples from endemic arsenosis areas were analyzed with INAA, EMPA, SEM-EDX, LTA, XRD, XAFS, and sequential leaching experiment. Arsenic in pyrite is from under the limit of EMPA to 1.75%, and in most cases, the content of arsenic is lower than 0.5%. Besides pyrite and arsenopyrite, SEM-EDX combined with LTA and XRD find that sulfates, clay and phosphates also contain arsenic. XAFS shows that arsenic mainly exists in the form of As^5＋. More than 50% of arsenic stayes in residual solid and combined with organic matrix in two samples, but most arsenic is leached out in other samples. The occurrence of such exceptionally high As contents in coal and the fact that the arsenic is dominantly organically associated are unique observations.

Composition and mode of occurrence of minerals in Late Permian coals from Zhenxiong County,northeastern Yunnan,China

Minerals in the Late Permian coals from the Niuchang-Yigu mining area,Zhenxiong County,northeastern Yunnan,China,were investigated using optical microscopy and low temperature ashing plus X-ray diffraction(LTA?XRD).The results showed that minerals in the coal LTAs are mainly quartz,kaolinite,chamosite,mixed-layer illite/smectite(I/S),pyrite,and calcite,with trace amounts of marcasite,dolomite,and bassanite.The authigenic quartz generally occurs in collodetrinite or as a filling in cleats or cell cavities.This silica was mainly derived from aqueous solutions produced by the weathering of basaltic rocks in the Kangdian Upland and from hydrothermal fluids.The presence of b-quartz paramorph grains in collodetrinite probably indicates that these grains were detrital and came from a volcanic ash.Clay minerals are generally embedded in collodetrinite and occur as cell-fillings.Pyrite occurs as framboidal,anhedral,and euhedral grains and a cell-filling.The coals are high in pyrite and the high pyrite content probably results from seawater invading during the stage of peat accumulation.Calcite generally occurs as vein-fillings,indicating an epigenetic origin.

Physicochemical,mineralogy,and thermo-kinetic characterisation of newly discovered Nigerian coals under pyrolysis and combustion conditions

In this study,the physicochemical,microstructural,mineralogical,thermal,and kinetic properties of three newly discovered coals from Akunza(AKZ),Ome(OME),and Shiga(SHG)in Nigeria were examined for potential energy recovery.Physicochemical analysis revealed high combustible but low levels of polluting elements.The higher heating values ranged from 18.65 MJ/kg(AKZ)to 26.59 MJ/kg(SHG).Microstructure and mineralogical analyses revealed particles with a rough texture,surface,and glassy lustre,which could be ascribed to metals,quartz,and kaolinite minerals.The major elements(C,O,Si,and Al),along with minor elements(Ca,Cu,Fe,K,Mg,S,and Ti)detected are associated with clays,salts,or the porphyrin constituents of coal.Thermal analysis showed mass loss(ML)ranges from 30.51%to 87.57%and residual mass(RM)from 12.44%to 69.49%under combustion(oxidative)and pyrolysis(non-oxidative)TGA conditions due to thermal degradation of organic matter and macerals(vitrinite,inertinite and liptinite).Kinetic analysis revealed the coals are highly reactive under the oxidative and non-oxidative conditions based on the Coats-Redfem Model.The activation energy(Ea)ranged from 23.81 to 89.56 kJ/mol,whereas the pre-exponential factor(kQ)was from 6.77×10^(-4)/min to 1.72×10^(3)/min under pyrolysis and combustion conditions.In conclusion,the coals are practical feedstocks for either energy recovery or industrial applications.

Significant Mercury Isotope Anomalies in Hydrothermal Altered Coals from the Huaibei Coalfield,China

Igneous intrusion into coal-bearing strata can cause an abrupt increase of temperature-pressure and trigger hydrothermal circulation at the igneous rock-coal contact zone. The conductive heat of intruded lnagma and convective migration of secondary hydrothermal fluids have been observed to significantly alter the concentrations and modes of occurrence of mercury （Hg） in thermally-intruded coals.

Insights from principal component analysis applied to Py-GCMS study of Indian coals and their solvent extracted clean coal products

The present work aims at studying five Indian coals and their solvent extracted clean coal products using Py-GCMS analysis and correlating the characterization data using theoretical principal component analysis.The pyrolysis products of the original coals and the super clean coals were classified as mono-,di-and tri-aromatics,while other prominent products that were obtained included cycloalkanes,n-alkanes,and alkenes ranging from C_(10)-C_(29).The principal component analysis is a dimensionality reduction technique that reduced the number of input variables in the characterization dataset and gave inferences on the relative composition of constituent compounds and functional groups and structural insights based on scores and loading plots which were consistent with the experimental observations.ATR-FTIR studies confirmed the reduced concentration of ash in the super clean coals and the presence of aromatics.The Py-GCMS data and the ATR-FTIR spectra led to the conclusion that the super clean coals behaved similarly for both coking and noncoking coals with high aromatic concentrations as compared to the raw coal.Neyveli lignite super clean coal was found to show some structural similarity with the original coals,whereas the other super clean coals showed structural similarity within themselves but not with their original coal samples confirming the selective action of the e,N solvent in solubilizing the polycondensed aromatic structures in the coal samples.

Geochemistry of Sulfur and Hazardous Elements in Late Paleozoic Coals and Partings from Taozao Coalfield, Shandong Province, China

The analyses of different sulfur forms, the trace elements in pyrites using electron microprobe and the trace elements in coal using INAA (instrumental neutron activation analysis) of the Late Paleozoic coals from the Taozao coalfield in Shandong Province, China, conclude that most sulfur (>75 %) in high-sulfur coal of Taiyuan Formation occurred as pyrite, in which many hazardous elements co-existed and their concentrations varied with their geological origin. The concentrations of hazardous elements in high-sulfur coals from Taiyuan Formation, composing mainly of Cu, As, U, Pb, Mo and Co, are much higher than those in the low-sulfur coals from Shanxi Formation and Shihezi Formation, because the influence of seawater during and after coal accumulation in Taiyuan Formation is stronger than those in Shanxi and Shihezi formations. Moreover, the element As is related to Fe, and both elements exist mainly in the form of pyrite. The element U is richer in the coal influenced by seawater. In addition, the coal affected by the magmatism contains more U, too. When high-sulfur coals are processed with heavy media washing to remove sulfur and minerals, the majority of hazardous elements will also be removed from the coals.

Quality of Some Nigerian Coals as Blending Stock in Metallurgical Coke Production

Two Nigerian coals, Lafia-Obi and Chikila were blended in the mass ratio of 70:30 with imported American and Polish coking coals. Proximate analysis, free swelling index, Ruhr dilatometer and Gieseler plastometer were used in assessing the coking qualities of both the single coals and the blends. The results show that the blends are lower in moisture and ash contents;higher in volatile matter and fixed carbon than the single Nigerian coals. The rheological parameters revealed superiority in thermo-plastic properties of the blends over the unblended local coals. Lafia-Obi/Foreign coals blends possess lower ash and better rheological properties compared to Chikila/Foreign coal composites which have high ash and poor rheological properties. These together suggest that amongst the two Nigerian coals, Lafia-Obi is superior for blending with the foreign ones in metallurgical coke production.

Characterization of Tars from the Thermal Processing of Baganuur and Tavan Tolgoi Coals from Mongolia, Using SEC, UV-F, IR and Mass Spectrometry

Tars from two Mongolian coals (Tavan Tolgoi and Baganuur) produced by simple distillation have been characterized using size exclusion chromatography (SEC) with elution in both 1-methyl-2-pyrrolidinone (NMP) and a mixed solvent (NMP and chloroform), UV-fluorescence in chloroform and NMP, gas chromatography (GC), mass spectrometry (GC-MS, probe-MS and LD-MS with thin layer chromatography) and infra-red spectroscopy. The SEC chromatograms using NMP and the solvent mixture NMP: chloroform indicates that similar conclusions can be drawn from using either eluent. The synchronous UV-fluorescence spectra were shifted to longer wavelengths in chloroform solution than in NMP and chloroform may be the better solvent for these tars prepared without extensive secondary thermal treatment. Infra-red spectra indicated differences between the two coal tars that reflected their different ranks, with more oxygenate groups in the lower rank Baganuur coal. Mass spectrometry (GC-MS and probe-MS) of both coal tars confirmed the presence of aliphatic components as well as aromatics and the relatively extensive alkylation of aromatics. Molecular mass ranges indicated for Baganuur tar by SEC compared well with the mass range by LD-MS although the LD-MS extended to higher mass values. The high mass fractions of the tars were revealed by fractionation by thin layer chromatography with the relevant sections of the developed plates inserted directly into the mass spectrometer;laser desorption was directly from the surface of the plate. LD-MS of the unfractionated samples failed to detect the high mass components because of mass discrimination effects. The high mass components were carried over in the distillation by mass transfer of vapours into the condenser.

Ultimate Composition of Main Chinese Power Coals

Calculations and analyses are made for the ultimate composition of 158 Chinese power coals. The results reveal that the carbon content on as received basis, Cr, increases linearly with the increase of the low heating value Qnot,a, on as received basis; the hydrogen content on as received basis, Hr, first increases with the increase of the volatile content on dry ash free basis Vdaf （Vdaf 〈 33.0%） and then decreases （Vdaf 〉 33.0%）; the oxygen content on as received basis, Oar, increases linearly with the increase of Vau, ranging between 2.0% and 12.5%. By comparison, the nitrogen content on as received basis N of bituminous and lean coal is higher, while the sulfur content on as received basis Sar Of anthracite is higher than bituminous coal, lean coal and lignite. The hydrogen on as received basis Hr is important for the conversion between low heating value and high heating value on as received basis for Chinese power coals, and Sr is important for the calculation of high heating value from the oxygen bomb heat value for Chinese power coals.

Compositional and Structural Study of Macerals in Coals and Source Rocks Using SIMS

The authors applied the Secondary Ion Mass Spectrometry (SIMS) technique to the analysis of compositions and structures of vitrinites fusinites, fusinites bitumens and graptolites in the hydrocarbon source rocks with different maturities dscribed their SIMS spectral characteristics and found that different macerals have differnt spectra which, reflected the compositional and structural differences of macerals. Moreover, the change bod of parameter CH2+/CH3+ can be used for the evaluation of thermal evolution regularity of macerals in the hydrocarbon source rocks The study results show that the SIMS technique is a powerful means for microara analysis of macerals in coals and source rocks. It is certain that the study level of macerals can be raised by detailed study of SIMS results of SIMS results of macerals.

Distributions of rare-earth elements in two Chinese coals and their burnt products

The concentrations of two fresh Chinese coals (lignitie and fatty coal ) from dif-ferent geological origin and the corresponding fly and bottom ashes were determined us-ing inductively coupled plasma mass spectrometry(ICP-MS). The ranges and means of concentrations of these elemennts were given. Based on the combustion simulating ex-periment in the one-dismensional boiler, the contents of REE (rare-earth element) of 18 samples in lignite, fatty coal and their fly and bottom ashes in different combustion condi-tion were determined, and geochemical feature of REE were analyzed.

The concentration of fluorine in coals and gangue of China

A detailed comparison was done between the data about the F in coals published at home and abroad, and associated with the special situation in China. An introduction also was made to illuminate the forming, occurrence and accumulation of the F in coals and its potential hazard to human and environment. Analytical data of coal samples were referred to study the great difference of the F content between coals and gangue. The results show that the average value of the F in the coal samples collected in different coalfields of China is 304x10^6, while that of gangue samples is surprisingly 1 319x10^6, especially the F content of coal ash from Bangmai in Yunnan Province reaches 4 800x10^6. It has been proved in many provinces of China that burning the coal and clay mixture can produce F contamination.