Study on the pyrolysis behavior of Shendong Shangwan coal and its macerals concentrate

The pyrolysis characteristics of Shendong Shangwan coal and its macerals concentrate were investigated using thermogravimetry （TG） coupled with mass spectrometry （MS）. The evolved gases were analyzed online by MS spectroscopy. The results of TG/DTG （derivative thermogravimetry） show ths vitrinite concentrate has greater weight loss rate and higher volatile yield than the other two samples. More light hydrocarbons C1-C5 are released from the vitfinite concentrate than from the Shendong Shangwan coal and inertinite concentrated in the process of pyrolysis. Three samples have similar shape curves of evolved gases of C2~C5 with different intensities. When the pyrolysis temperature was lower than 418℃, the amount of C6H6 evolved in the process of pyrolysis of inertinite concentrated was higher than that of raw coal and vitrinite concentrate. As the temperature rising, the production rate of C6H6 increased. Below 672℃, C6H6 evolution rate of vitrinite concentrate was far greater than the other two samples; the main evolution temperature range of C7H8 was 400℃ to 700℃ for the three samples. The amount of HE and H20 released first increased and then decreased with the temperature increase while more H2 released for pyrolysis of inertinite concentrated and more H20 released for the pyrolysis of vitrinite concentrate.

Study of Pyrolysis Characteristics and Kinetic Analysis of Shenmu Coal at a High Heating Rate Using TG-FTIR

Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.

Effect of demineralization on pyrolysis characteristics of LPS coal based on its chemical structure

The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.

Research on the maceral characteristics of Shenhua coal and efficient and directional direct coal liquefaction technology

In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.

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.

Preparation and coking properties of coal maceral concentrates

The concentrates with different maceral contents were obtained from Kailuan coking coals with different coal ranks(Ro;ranvarying from 0.88%to 1.73%)by float–sink separation in lab.Then these concentrates were characterized by proximate analysis,ultimate analysis,petrography analysis and coking index determination.The results show that the vitrinite is characterized as nature of lower carbon content,higher hydrogen content,higher volatile matter and stronger caking property compared to inertinite.The relationships between variation rate of volatile matter and maximum volatile matter and coal ranks are identified,and a linear model is developed for fast determination of the maceral contents.Compared to inertinite-rich concentrate,the blending ratio of vitrinite-rich concentrate is increased by 13%,which is considered to be a potential technique based on maceral separation for expanding the coking coal resources.

Combustion characteristics of semicokes derived from pyrolysis of low rank bituminous coal

Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.

Flotation characteristics of Shenfu coal macerals

The flotation characteristics of Shenfu coal macerals was researched. Taking flotation recovery and enrichment of macerals as the evaluation objects, the influence of the agent dosage, pulp concentration, impeller speed and aeration rate on the separating effect was investigated. And the optimum process conditions of flotation were confirmed. The results show that the agent dosage, pulp concentration, impeller speed and aeration rate have a significant impact on flotation recovery and en- richment of macerals. The float recovery was 73.28% and enrichment ratio of vitrinite was 83.89% when CTAB dosage of 1.0 kg/t, pulp concentration of 100 g/L, impeller speed of 1 700 r/min and aeration rate of 0.25 m3/（m2·min） were used. The tailings yield was 60.30% and enrichment ratio of inertinite was 61.44% when CTAB dosage of 0.5 kg/t, pulp concentration of 100 g/L, impeller speed of I 700 r/min and aeration rate of 0.20 m3/（m2·min） were used.

Carbon monoxide adsorptive capability of low rank coal's maceral

The centrifugal separation with gravity experiment was made for getting every pure macerals like inertinite and vitrinite,and the isothermal adsorption tests of pure mac- eral are carried out at 30,40,50,55,60,65℃,respectively,after analyzing the proximate element and maceral of coal samples,which was aimed to study the CO adsorptive capa- bility of every maceral of low rank coal at difference temperature and pressure.The results show that the adsorption isotherm of CO can be described by Langmuir equation because it belongs to the Type I adsorption isotherm at low temperature(T≤50℃),and the tem- perature effect on coal adsorption is greater than of pressure in lower temperature and pressure area;what's more,the relationship is linear between the coal adsorption quantity of CO and the pressure at high temperature(T>50℃),it can be described by Henry equation(Q=KP),which increases with pressure.Both temperature and pressure has great influence on CO adsorptive capability of low rank coals,especially the temperature's effect is so very complex that the mechanism need to study further.At the same time,the volatile matter,inertinite,oxygen-function groups and negative functional groups are high popu- larly in low rank coal samples,especially,the content of hydroxide(-OH) has great influ- ence on CO adsorption in that the inertinite has stronger effect than vitrinite on adsorptive capability of low rank coal samples,the result is same to the research on CH4 adsorption.

Influences of Temperature and Coal Particle Size on the Flash Pyrolysis of Coal in a Fast-entrained Bed

The experiments on the flash pyrolysis of a lignite were carried out in a fast-entrained bed reactor as a basic study on a so-called ＇ coal topping process＇. The investigation focused on the effects of pyrolysis temperature and coal particle size on the product distribution and composition. The experimental results show that an increase in the pyrolysis temperature results in a higher yield of gaseous products while a larger particle size leads to a decrease of the liquid yield. An optimum temperature for the liquid yield was found to be 650℃. A certain amount of phenol groups was found in the liquid products, which may be used to produce high-valued fine chemicals. The FTIR analyses of the coal and chars show that aliphatic structures in the chars are gradually replaced by aromatic structures with the increasing of pyrolysis temperature and coal particle size. The results of this study provide fundamental data and optimal conditions to maximize light oils yields for the coal topping process.

Paleo-fires and Atmospheric Oxygen Levels in the Latest Permian:Evidence from Maceral Compositions of Coals in Eastern Yunnan,Southern China

Inertinite maceral compositions of the Late Permian coals from three sections in the terrestrial and paralic settings of eastern Yunnan are analyzed in order to reveal the paleo-fire events and the atmospheric oxygen levels in the latest Permian. Although the macerals in the studied sections are generally dominated by vitrinite, the inertinite group makes up a considerable proportion. Its content increases upward from the beginning of the Late Permian to the coal seam near the Permian- Triassic boundary. Based on the microscopic features and the prevailing theory that inertinite is largely a by-product of paleo-fires, we suggest that the increasing upward trend of the inertinite abundance in the latest Permian could imply that the Late Permian peatland had suffered from frequent wildfires. Since ignition and burning depend on sufficient oxygen, a model-based calculation suggests that the 02 levels near the Wuchiapingian/Changhsingian boundary and the Permian-Triassic boundary are 27% and 28% respectively. This output adds supports to other discoveries made in the temporal marine and terrestrial sediments, and challenges the theories advocating hypoxia as a mechanism for the PermianTriassic boundary crisis.

A density functional theory study on the decomposition of aliphatic hydrocarbons and cycloalkanes during coal pyrolysis in hydrogen plasma

To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.

CFD Simulation of a Hydrogen/Argon Plasma Jet Reactor for Coal Pyrolysis

A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete data, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-εequations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.

Influence of heating rate on reactivity and surface chemistry of chars derived from pyrolysis of two Chinese low rank coals

A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.

Infrared Spectra and Pyrolysis of Selected Molecular Models of Coal: Insight from Density Functional Calculations

Equilibrium structures and infrared spectra of four typical molecular models of coal have been studied by density functional calculations. Combining theoretical calculations on the coal models with experimental FT-IR spectra of selected low rank perhydrous coals, a plausible molecular representation for this kind of coals was proposed, and its predicted IR spectra reasonably match the experimental observation. Calculations indicate that the cleavage of the C-C bridge bond for the coal structures considered here occurs at about 540 ℃ and the C-O ether bridge bond may break under temperature ranging from 500 to 600 ℃for the aryl-CH2-O-CH2-aryl ether bond or from 200 to 300 ℃ for the aryl-CH2-O-aryl ether bond, showing remarkable effect of the local structural environment. The coal model containing the carboxyl group may release CO2 at about 300 ℃ through the decarboxylation with a barrier of 69 kcal/mol.

Effects of calcium on the evolution of nitrogen during pyrolysis of a typical low rank coal

This study aims to investigate the effects of calcium on the migration of nitrogen in coal(coal-N)to N-containing gas species,particularly,NH3 and HCN(volatile-N)in volatiles,as well as the chemical transformation of the N in char during coal pyrolysis under different temperatures.The pyrolysis experiments of Shengli brown coal and its derived coal samples loaded with different contents of calcium were conducted under 600–800°C in a novel fluidized bed reactor.The experimental results showed that during coal pyrolysis,the generation of NH3 is mainly derived from secondary reactions among volatiles,tar and char with the catalytic effect of mineral matter,especially calcium in coal.Increasing pyrolysis temperature from 600 to 800°C could enhance the release of N in coal to volatiles.Meanwhile,the increased pyrolysis temperature could also inhibit the generation of NH3 while facilitating the formation of HCN.The release of HCN is more sensitive to pyrolysis temperatures.Specifically,under higher pyrolysis temperatures,more N-containing structures in coal would become thermally unstable and crack into HCN;On the other hand,higher pyrolysis temperature could also enhance the decomposition of N in coal to N-containing species in tar or N2,thus reducing the release of HCN and NH3.Nitrogen in tar could either undergo secondary decomposition reactions,generating NH3,HCN,N2 and other N-containing species in gas phase,or experience condensation polymerization by forming macromolecular structure and be retained in char at high pyrolysis temperatures.Calcium could significantly restrain the release of N from coal,thus reducing the yields of NH3 and HCN.During coal pyrolysis,calcium catalytically enhances the fracture and combination of chemical bonds,generating abundant free radicals.These free radicals could continuously attack N-containing structures and consequently release the N-containing gaseous products,such as NH3,HCN,N2 etc.,resulting in the decrease of N in char.Calcium also plays important roles in nitrogen transformation in char during coal pyrolysis by catalytically intensifying the transformation of N in char from pyridinic nitrogen(N-6)and pyrrolic nitrogen(N-5)to quaternary type nitrogen(N-Q)during coal pyrolysis.

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.

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.

Geochemical characteristics of different maceral groups in the Huangxian Coal,China

In order to research how lignite is utilized, two coal samples of seams 2 and 4 were taken from the Huangxian Basin, China. The samples were separated into vitrinite, sporinite, and resinite. Geo-chemical and pyrolysis methods were used to analyse three maceral groups and two seam samples. The results indicate that the resinite and sporinite groups have higher extract yields, S1, S2, HI values, and pyrolysis compounds. These differences may shed light on the usage of the Huangxian lignite. Seam 2 pro- duces more gas and oil than seam 4 does because seam 2 contains more resinite and sporinite macerals.

Enhanced near-zero-CO2-emission chemicals-oriented oil production from coal with inherent CO2 recycling: Part I—PRB coal fast pyrolysis coupled with CO2/CH4 reforming

In this study,the Powder River Basin(PRB)coal fast pyrolysis was conducted at 700°C in the atmosphere of syngas produced by CH4-CO2 reforming in two different patterns,including the double reactors pattern(the first reactor is for syngas production and the second is for coal pyrolysis)and double layers pattern(catalyst was at upper layer and coal was at lower layer).Besides,pure gases atmosphere including N2,H2,CO,H2-CO were also tested to investigate the mechanism of the coal pyrolysis under different atmospheres.The pyrolysis products including gas,liquid and char were characterized,the result showed that,compared with the inert atmosphere,the tar yield is improved with the reducing atmospheres,as well as the tar quality.The hydrogen partial pressure is the key point for that improvement.In the atmosphere of H2,the tar yield was increased by 31.3%and the contained BTX(benzene,toluene and xylene)and naphthalene were increased by 27.1%and 133.4%.The double reactors pattern also performed outstandingly,with 25.4%increment of tar yield and 25.0%and 79.4%for the BTX and naphthalene.The double layers pattern is not effective enough due to the low temperature(700°C)in which the Ni-based catalyst was not fully activated.