Formation of mesophase microbeads from bulk mesophase pitch induced by fullerene

A transformation of naphthalene-based coalescenced mesophase pitch(NMP)to mesophase microbeads was achieved by heating a mixture of NMP and fullerene(C_(60)).This is different from the conventional process of the liquid-phase carbonization of isotropic pitch to the emergence of carbon microbeads in the matrix and finally their growth to form a 100%anisotropic bulk meso-phase,but rather a reverse transformation.The effects of C_(60) loading and reaction temperature on the morphological transformation of mesophase were investigated by polarizing optical and scanning electron microscopies.The physical changes in the NMP induced by C_(60) were characterized by thermogravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffractometry and Raman spectroscopy.The results show that the coalesced NMP can be converted to a spherical type at 300-320℃ with the addition of 5%C_(60),and the size of the mesophase microbeads increases with increasing temperature.Furthermore,a model is established to ex-plain the unique induction effect of C_(60) in the transformation process.This work makes the morphological transformation of MP con-trollable,and provides a new idea for the understanding and research of mesophase pitch.

Semi-quantitative analysis of the structural evolution of mesophase pitch-based carbon foams by Raman and FTIR spectroscopy

Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.

A review of the catalytic preparation of mesophase pitch

Because of its high purity and excellent orientation, mesophase pitch is a superior precursor for high-performance car-bon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic polycondensation at low temperat-ures is more favorable for synthesizing mesophase pitch, because it circumvents the high-temperature free radical reaction of other thermal polycondensation approaches. The reaction is gentle and can be easily controlled. It has the potential to significantly im-prove the yield of mesophase pitch and easily introduce naphthenic characteristics into the molecules, catalytic polycondensation is therefore a preferred method of synthesizing highly spinnable mesophase pitch. This review provides a synopsis of the selective pre-treatment of the raw materials to prepare different mesophase pitches, and explains the reaction mechanism and associated research advances for different catalytic systems in recent years. Finally, how to manufacture high-quality mesophase pitch by using a cata-lyst-promoter system is summarized and proposed, which may provide a theoretical basis for the future design of high-quality pitch molecules.

Texture development of mesophase in reservoir pyrobitumen and the temperature-pressure converting of the gas reservoir in the Chuanzhong Uplift, Southwestern China

The Neoproterozoic-Lower Paleozoic dolostone gas reservoirs in the Chuanzhong Uplift in Southwestern China contain the mesophase pyrobitumen (pyrobitumen with mesophase). The mesophase in the pyrobitumen is mostly composed of a mixture of condensed macromolecule polycyclic aromatic hydrocarbons (PAH), and has been mostly converted to various grain, flow, and domain textures. The volcanic activity nearby the Chuanzhong Uplift may have generated very hot (over 300 °C) hydrothermal fluid, with migration of the fluid into the dolostone reservoir transforming the hydrocarbons in the reservoir into an anisotropic carbon by-product, which formed under high temperature and pressure conditions;over 300 °C and 200 MPa according to fluid inclusion analysis. The high temperature-pressure in reservoir was caused by sudden devolatilization of the hydrocarbons due to hydrothermal heating, which formed the unusual texture of the mesophase. The elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen deposits are all unusual textures. This study investigates the texture development of this pressure-affected pyrobitumen. Observation and study of the mesophase suggest that the class of mesophase in pyrobitumen is determined by temperature, while pressure (assessed from associated fluid inclusions) significantly affected the texture. Analysis of the texture of the pyrobitumen in conjunction with previous thermometry results from methane inclusions suggests that the high class mesophase of the pyrobitumen could be applied as a temperature indicator for geological conditions. Furthermore, the unusual textures of the pyrobitumen including elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen could reflect the abnormal high formation pressure.

Tunable and efficient microwave absorption from mesophase pitch carbide with designable electromagnetic properties

In order to obtain the microwave absorption(MA)materials with light weight,high efficiency and tunable properties,the carbonized mesophase pitch(CMP)with the variation in carbonization temperatures and particle sizes were prepared and characterized.The carbonization temperature mainly controlled the graphitization degree of the CMP to affect their conductive loss.The carbon residues were generated on the CMP surface when the temperature was higher than 700℃,which contributed significantly to the polarization loss of the CMP.For scale regulation,the segregation between the particles in the paraffin ring caused by the reduction particles of CMP carbonization at 750℃(750 CMP)resulted in a significant reduction in conductive losses while improving their impedance matching.The 750 CMP over 300 mesh sieved had the strongest MA properties of-53 d B at 3.4 GHz within 5.5 mm.Moreover,the prepared CMPs were multi-layer compounded and optimized by CST microwave studio.The synergistic effect derived from the improved impedance matching and the enhanced interfacial polarization resulted in significant reflection loss in multi-layer CMP.Overall,these findings lead to the systematically regulation of carbon-based materials for MA,showing an attractive application prospect for the preparation of high-performance MA materials.

Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Coal-based reduction mechanism of low-grade laterite ore

A low-grade nickel laterite ore was reduced at different reduction temperatures. The morphology of metallic particles was investigated by scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS）. Experimental results indicate that the metallic nickel and iron gradually assemble and grow into larger spherical particles with increasing temperature and prolonging time. After reduction, the nickel laterite ore obviously changes into two parts of Fe-Ni metallic particles and slag matrix. An obvious relationship is found between the reduction of iron magnesium olivine and its crystal chemical properties. The nickel and iron oxides are reduced to metallic by reductant, and the lattice of olivine is destroyed. The entire reduction process is comprised of oxide reduction and metallic phase growth.

A review of the synthesis and application of zeolites from coal-based solid wastes

Zeolite derived from coal-based solid wastes(coal gangue and coal fly ash)can overcome the environmental problems caused by coal-based solid wastes and achieve valuable utilization.In this paper,the physicochemical properties of coal gangue and coal fly ash are introduced.The mechanism and application characteristics of the pretreatment processes for zeolite synthesis from coal-based solid wastes are also introduced.The synthesis processes of coal-based solid waste zeolite and their advantages and disadvantages are summarized.Furthermore,the application characteristics of various coal-based solid waste zeolites and their common application fields are illustrated.Finally,we propose an alkaline fusion-assisted supercritical hydrothermal crystallization as an efficient method for synthesizing coal-based solid waste zeolites.In addition,more attention should be given to the recycling of alkaline waste liquid and the application of coal-based solid waste zeolites in the field of volatile organic compound adsorption removal.

Structural Characteristics of Mesophase Spheres Prepared from Coal Tar Pitch Modified by Phenolic Resin

Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.

Migration behaviors and kinetics of phosphorus during coal-based reduction of high-phosphorus oolitic iron ore

To understand the migration mechanisms of phosphorus(P)during coal-based reduction,a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions.The migration characteristics and kinetics of P were investigated by a field-emission electron probe microanalyzer(FE-EPMA)and using the basic principle of solid phase mass transfer,respectively.Experimental results showed that the P transferred from the slag to the metallic phase during reduction,and the migration process could be divided into three stages:phosphorus diffusing from the slag to the metallic interface,the formation of Fe P compounds at the slag metal interface and P diffusing from the slag metal interface to the metallic interior.The reduction time and temperature significantly influenced the phosphorus content of the metallic and slag phases.The P content of the metallic phase increased with increasing reduction time and temperature,while that of the slag phase gradually decreased.The P diffusion constant and activation energy were determined and a migration kinetics model of P in coal-based reduction was proposed.P diffusion in the metallic phase was the controlling step of the P migration.

In Situ Synthesis of NaY Zeolite with Coal-Based Kaolin

NaY zeolites were in-situ synthesized from coal-based kaolin via thehydrothermal method. The effects of various factors on the structure of the samples were extensivelyinvestigated. The samples were characterized by N_2 adsorption, XRD, IR and DTG-DTA methods, andthe results show that the crystallization temperature and amount of added water play an importantrole in the formation of the zeolite structure. The 4A and P zeolites are the competitive phasepresent in the resulting product. However, NaY zeolites with a higher relative crystallinity,excluding impure crystals and the well hydrothermal stability, can be synthesized from coal-basedkaolin. These zeolites possess a larger surface area and a narrow pore size distribution, and thismeans that optimization of this process might result in a commercial route to synthesize NaYzeolites from coal-based kaolin.

Mesophase formation of coal-tar pitches used for impregnant of C/C composites

By a polarized light optical microscopy with a hot stage, liquid phase nuclear magnetic resonance 13 C NMR and 1 H NMR, X ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formation of mesophase in C/C composites, such as pressure, quinoline insolubles (QI) and heterocylic compounds, were analyzed. Further, the graphitizability of the resultant carbon was discussed. The results indicate that to some degree, QI contents accelerate the formation of mesophase at atmospheric pressure; while at high pressure, the coalescence and growth of mesophase spherules are impeded and the resultant coke produced from higher QI content pitch is harder to be graphitized. This is in agreement with the transfer of microstructure from domain anisotropy to fine grained mosaics.

Study on methanol synthesis from coal-based syngas

The intrinsic kinetic models of the Langmuir-Hinshelwood type were investigated in terms of the reaction rates of CO hydrogenation and CO_2 hydrogenation in theform of reactant fugacity. The parameters were estimated by the Universal Global Optimization using the Marquardt method. Residual error distribution and statistic tests show thatthe intrinsic kinetic models are reliable and acceptable. The mathematic model of a combined converter formed by gas-cooled and water-cooled reactor was developed and thegas-cooled reactor and the water-cooled reactor were characterized with one-dimensionalmathematic model. The distributions of temperature and concentration in the catalytic bedof the gas-cooled reactor and the water-cooled reactor in a combined converter with ayield of 1.2 Mt/a were simulated. The parallel cross linking pore model was used to describe the transfer process of multi-component diffusion system in the catalyst. The calculated value computed by the internal diffusion efficiency factor calculation model established for methanol synthesis catalyst fit the experimental value very well.

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.

Adsorption and Regeneration of Volatile Organic Compounds(VOCs)on Coal-Based Activated Carbon by Ferric Nitrate Modification

In this study,the Heishan coal was used to prepare a series of activated carbon(AC)samples via a vapor deposition method.The effects of the Fe(NO_(3))3/coal weight ratio on the physicochemical properties of the activated carbon were systematically investigated,and the AC samples were analyzed by the N2 adsorption-desorption technique,the scanning electron microscopy,the X-ray diffraction,the Raman spectroscopy,and the Fourier transform infrared spectroscopy.Furthermore,the adsorption properties of ethyl acetate were investigated.The results indicated that as the Fe(NO_(3))3/coal mass ratio increased from 1:8 to 1:2,the specific surface area,the total pore volume and the micropore volume initially increased and then decreased.The specific surface area increased from 560.86 m^(2)/g to 685.90 m^(2)/g,and then decreased to 299.56 m^(2)/g.The total pore volume and micropore volume increased from 0.29 cm^(3)/g and 0.17 cm^(3)/g to 0.30 cm^(3)/g and 0.22 cm^(3)/g,and then decreased to 0.16 cm^(3)/g and 0.10 cm^(3)/g,respectively.The optimized ratio was 1:8.During the activation process,iron ions infiltrated the activated carbon to promote the development of the pore structure,the pore size of which was between 2.5 nm and 3 nm in daimeter.This approach could enhance the capacity for adsorption of ethyl acetate.It is worth noting that the ACs displaying the largest specific surface area and total pore volume(685.90 m^(2)/g and 0.30 cm^(3)/g)were formed under the optimized activation conditions(950℃,20%(volume)of CO_(2),ratio 1:5),and the maximum AC capacity for adsorption of ethyl acetate was 962.62 mg/g.After seven repeated thermal regeneration experiments,the saturated AC adsorption capacity was still above 90%.

Preparation of activated carbons from mesophase pitch and their electrochemical properties

The influences of molar ratio of KOH to C and activated temperature on the pore structure and electrochemical property of porous activated carbon from mesophase pitch activated by KOH were investigated. The surface areas and the pore structures of activated carbons were analyzed by nitrogen adsorption, and the electrochemical properties of the activated carbons were studied using two-electrode capacitors in organic electrolyte. The results indicate that the maximum surface area of 3 190 m2/g is obtained at molar ratio of KOH to C of 5:1, the maximum specific capacitance of 122 F/g is attained at molar ratio of KOH to C of 4:1, and 800 ℃ is the proper temperature to obtain the maximum surface area and capacitance.

Purification process of coal-based coke powder as anode for Li-ion batteries

A process of purification of coal-based coke powder as anode the treatment of coke powder with dilute hydrofluoric acid solution, for Li-ion batteries was attempted. The process started with followed by united-acid-leaching using sulfuric acid and hydrochloric acid. The effects of altering the hydrofluoric acid addition, hydrofluoric acid concentration, contact time, temperature and acid type were investigated. A minimum ash content of 0.35% was obtained when proper conditions were applied. The electrochemical performance of purified coke powder shows greatly improved electrochemical performance. The as-purified coke powder presented an initial reversible capacity of 257.4 mAh/g and a retention rate of 95% after 50 cycles. The proposed purification process paves a way to prepare a promising anode material with good performance with low cost of coke powder for Li-ion batteries.

Evaluation of Molecular Structural Effects on Needle Coke Mesophase Stacking

Molecular simulations were performed to investigate the molecular structural effects on needle coke mesophase stacking.The simulation results showed that the stacking states of anthracene trimer and tetramer accumulations were orderly,while the stacking states of anthracene dimer,pentamer,and hexamer accumulations were disorderly.Anthracene trimer and tetramer in the model compounds were two of the most ideal needle coke mesophase constituents.It was also found that the introduction of methyl side chains in anthracene trimer derivatives was not conducive to the formation of a mesophase crystal.To sum up,the molecules which had similar structures to anthracene trimer or tetramer with no alkyl chains are ideal constituents of needle coke mesophase.

Effect of reducing agents on reducing atmosphere in coal-based direct reduction of beach titanomagnetite

Beach titanomagnetite(TTM)provides a cheap alternative source of Fe and Ti,but this ore is difficult to process to make suitable concentrates for the blast furnace.Recently studies showed that it is feasible to separate Fe and Ti by coal-based direct reduction.In this study,beach TTM was selected as the research object,the effects of reducing agents on reducing atmosphere in coal-based direct reduction of beach TTM were analyzed,and the role of volatiles was also studied.The results showed that when bitumite and coke were used as reducing agents of TTM,the CO produced from volatiles was involved in the reduction reaction,and the generated CO_(2) provided the raw material for the reaction of TTM.The reduction effect of bitumite was better than that of coke.The reason is that bitumite+TTM had a higher gas generation rate and produced a higher CO partial pressure,while coke+TTM had a lower gas generation rate and produced a lower CO partial pressure.When graphite was used as a reducing agent,there was a solid-solid reaction in the early stage in the reaction.With the continuous accumulation of CO_(2),the Boudouad reaction started and accelerated.Graphite+TTM also produced a higher CO partial pressure.

Carbonaceous mesophase spherule/activated carbon composite as anode materials for super lithium ion capacitors

A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the active carbon shell precursor.The structures of the composites were examined by scanning electron microscopy and X-ray diffractometry.The electrochemical performance was investigated in electric double layer capacitor and half-cell.The results show that,the composite exhibits good performance in both capacitor and battery with a high reversible capacity of 306.6 mA·h/g(0.2C) in the half-cell,along with a capacitance of 25.8 F/g in the capacitor when an optimum ratio of carbonaceous mesophase spherules to active carbon is adopted.The composite also shows a favorable rate performance and good cycle ability.A working model of this anode in super lithium ion capacitors was established.