Synthesis of hollow porous carbon nanospheres from coal tar for adsorption of Direct Black 38 dye

A hollow porous carbon nanospheres (HPCNs) material which suits for adsorption of Direct Black 38 (DB38) was prepared from coal tar using zinc acetate as a template coupled with KOH activation. The synthesized HPCNs features with nanospheres structure and contains both micropores and a lot of mesopores. The HPCN_1?4?2 made with the mass weight ratio of coal tar/zinc acetate/KOH at 1:4:2 shows a large surface area of 1374 m² g^?1 with an average pore size of 7.41 nm. The HPCN_1?4?2 exhibits excellent adsorption capacity for DB38 dye, which has big molecular size at room temperature. This is mainly due to its large surface area and pore volumes contributed by its mesopores. This work suggests an effective way to synthesize a high performance adsorbent for large molecular size dyes from low-cost coal tar.     

Enlargement of the micropores of a caking bituminous coal by controlled oxidation

In a study of the enlargement of pores of coals it has been found that treatment of a bituminous coal (PSOC No. 371, from the Pennsylvania State University Coal Section) with a 5:95 O₂:N₂ stream 4 h at 400 °C increases the surface area as measured by nitrogen adsorption at 77K by a factor of at least 50 to a value 52 m² g^?1. The increase in pore size was accompanied by a 9.7% weight loss. Simultaneously, the area as measured by carbon dioxide at 195K increased from 61 to 136 m² g^?1 and that measured by carbon dioxide at room temperature increased from 125 to 237 m² g^?1. Attempts to enlarge the pores by oxidation with hydrogen peroxide or ozone were unsuccessful. A Pittsburgh coal subject to a small percentage of oxygen in nitrogen or steam at 300 to 400 °C showed a surface area as measured by nitrogen adsorption of less than 1 m² g^?1 both before and after such pretreatment. This same coal with a 5:95 O₂:N₂ stream for 4 h at 450 °C showed a surface area of 110 m² g^?1 measured by nitrogen adsorption at 77K.     

CO2 separation by carbon molecular sieve monoliths prepared from nitrated coal tar pitch

The objective of the present work is to develop a simple procedure, which avoids the need of a binder, to obtain activated carbon monoliths from a waste precursor (coal tar pitch) suitable for CO₂ capture and/or separation. The main task of this process consists of a nitration process of the coal tar pitch. This nitration step over the coal tar pitch is characterised by different techniques, such as infrared spectroscopy and thermogravimetric analysis. The nitration treatment produces the oxidation of the pitch molecules, leading to hydrogen consumption and generating oxygenated and nitrogenated surface complexes. As a consequence of this oxidation, nitrated coal tar pitch is an infusible material, which allows the carbonization of monolithic pieces avoiding their fusion. Decomposition of these surface complexes during the carbonization of monoliths generates narrow microporosity, which is suitable for CO₂ capture from gas streams at room temperature. The molecular sieving properties of these materials are studied by CH₄ and CO₂ adsorption kinetics.     

Utilisation of the binders prepared from coal tar pitch and phenolic resins for the production metallurgical quality briquettes from coke breeze and the study of their high temperature carbonization behaviour

To reduce the cost of the formed coke briquettes which can be used as a substitute fuel to the metallurgical coke for the blast furnace from the coke breeze alternative binders and their blends were used. The high temperature behavior was investigated. The binders tested were: the nitrogen blown, air blown coal tar pitch and the blend of air blown coal tar pitch with the phenolic resins blends. The phenolic resin blends were prepared by mixing equal amount of resole and novalac. From the results, nitrogen blowing resulted in the weakest briquettes. The air blowing procedure should be preferred in place of nitrogen blowing for this purpose. When the air blown coal tar pitch was used alone as a binder, the briquettes must be cured at 200 °C for 2 h, then carbonized at a temperature above 670 °C. Since it requires higher temperature at carbonization stage, using air blown coal tar pitch alone as a binder was not economical. Therefore, the briquettes were prepared from the blended binder, containing air blown coal tar pitch and phenolic resins blend. The optimum amount of air blown coal tar pitch was found to be 50% w/w in the blended binder. Curing the briquettes at 200 °C for 2 h was found to be sufficient for producing strong briquettes with a tensile strength of 50.45 MN/m². When these cured briquettes were carbonized at temperatures 470 °C, 670 °C and 950 °C, their strength were increasing continuously, reaching to 71.85 MN/m² at the carbonization temperature of 950 °C. These briquettes can be used as a substitute for the metallurgical coke after curing; the process might not require un-economical high temperature carbonization stage.     

Preparation of semi-activated carbon fibers

Preparation of semi-activated carbon fibers (SACFs) using a precursor consisting of coal tar pitch and phenolic resin coated on glass fiber was investigated. Stabilization of the fiber structure by crosslinking both the phenolic resin and coal tar pitch was essential to achieving high surface areas during high temperature activation. The phenolic resin was cured by using aqueous catalyst (hydrochloric acid/formaldehyde) followed by oxidative stabilization of the pitch. A surface area of 1,206 m²/g based on the precursor was obtained through activation using carbon dioxide/steam at 880 ‡C. The pore size distribution was shown to be vary narrow using the Horvath-Kawazoe (HK) method.     

The effects of iron sulphide surface area variations on coal liquefaction

The purpose of this work was to determine the effects of surface area variations of iron sulphides on coal liquefaction. Several iron sulphides were synthesized including pyrites (FeS₂) with 46.6 wt% Fe, pyrrhotites (Fe_1?xS) with ~ 60 wt% Fe and iron-sulphur compounds of unknown composition. Surface areas of the synthetic pyrites varied from 2 to ? 10 m² g^?1, pyrrhotite surface areas were 6 and 10 m² g^?1, and the surface areas of the iron-sulphur compounds were 40 and 80 m² g^?1. These iron sulphides were tested for catalytic activity in tubing reactor runs with West Virginia Blacksville no. 2 coal and SRC-II heavy distillate. All these sulphides showed catalytic effects as compared to runs with only coal and solvent, although the effects were not as large as those obtained with a cobalt-molybdenum on alumina catalyst. Large differences in surface areas before reactor testing did not cause any significant differences in conversion. The results from an additional series of tubing reactor runs, which was carried out to determine how iron sulphide surface areas change during liquefaction, showed that the surface areas were drastically changed during the two-minute heat-up of the reactor. Robena pyrite with a surface area of 2.0 m² g^?1 and the iron-sulphur compound with a surface area of 80 m² g^?1 yielded iron sulphides with surface areas of 5.2 and 10.8 m² g^?1 after a two-minute heat-up to 425°C and subsequent one-minute quench.     

Coal based magnetic activated carbon as a high performance adsorbent for methylene blue

Coal based magnetic activated carbons (MACs) were prepared by using the two-stage carbonization and activation of coal in the presence of Fe₂O₃ as the magnetic source. Compared with the single-stage carbonization and activation, the two-stage temperature method was found to be efficient for the preparation of MACs with the high specific surface area and good magnetic properties in a lower alkali/carbon ratio. The as-synthesized MACs at optimized conditions exhibited specific surface areas of up to 2075 m²/g and optimal saturation magnetization of as high as 15.02 emu/g. Moreover, as an adsorbent, the efficiency of removing methylene blue (MB) from aqueous solutions is excellent. Based on MB adsorption behaviors at various conditions, including initial dye concentration, contact time and temperature, MACs prepared at optimized conditions exhibited a maximum equilibrium MB adsorption capacity of 871 mg/g. The data of adsorption kinetics and isotherms could be well fitted by using the pseudo-second-order equation and the Freundlich model. Importantly, MACs can be separated and recovered easily by applying a magnetic field. Therefore, the coal-based magnetic activated carbons might be a promising candidate of high efficiency, low cost for removal of organic dyes.     

Production of coal tar/petroleum pitch by the combined distillation of coal tar and heavy cycle oil at JSC Gubakhinskii Koks

Coal tar/petroleum pitch has been produced by the combined distillation of coal tar and heavy cycle oil from catalytic cracking, in industrial trials. In processing a 60: 40 mixture of those components, 306 t of pitch that meets the requirements for anode binder is produced. The benzo[a]pyrene content is lower in the petroleum–coal pitch than in regular coal pitch used in electrode production.     

Production of petro/coal tar pitch by joint distillation of coal tar and heavy pyrolytic oil

The properties of petro/coal tar pitch and distillate fractions obtained in the joint distillation of coal tar and heavy pyrolytic oil from ethylene production are described. The petro/coal tar pitch is particularly reactive in heat treatment and air-blowing. The petro/coal tar pitch may be used as less carcinogenic binder and impregnating electrode pitch.     

Investigating the dependence of light-absorption properties of combustion carbonaceous aerosols on combustion conditions

We performed controlled combustion experiments to investigate the dependence of the mass absorption cross-section (MAC) and absorption Ångström exponent (AAE) of combustion carbonaceous aerosol emissions on combustion conditions. Using benzene and toluene as fuels, we obtained a wide range of combustion conditions by varying the combustion temperature and equivalence ratio. We also used nitrogen as a passive diluent to tune the combustion conditions. We calculated MAC and AAE from multi-wavelength light-absorption measurements using a photoacoustic spectrophotometer and aerosol mass loadings estimated from thermal-optical analysis. Starting with relatively low-temperature and fuel-rich combustion conditions and progressively increasing the temperature and/or decreasing the equivalence ratio, we produced emissions with progressive change from weakly absorbing brown carbon (BrC) (MAC at 532?nm (MAC₅₃₂) = 0.24?m²/g and AAE = 8.6) to strongly absorbing BrC (MAC₅₃₂ = 2.1?m²/g and AAE = 3.1) to mixtures of black carbon (BC) and strongly absorbing BrC (MAC₅₃₂ = 7.7?m²/g and AAE = 1.5). These findings indicate that combustion conditions are important in dictating the light-absorption properties of the emitted aerosols. Furthermore, regardless of fuel type and combustion conditions, the emitted aerosols exhibit a unified continuum of light-absorption properties that can be characterized by MAC₅₃₂ and AAE pairs. The MAC₅₃₂ and AAE pairs are well-correlated with the elemental carbon-to-organic carbon ratio (EC/OC), which is a proxy of combustion conditions, confirming previous findings that EC/OC is a practical basis for parameterizing the light-absorption properties of combustion carbonaceous aerosols.

Copyright © 2019 American Association for Aerosol Research     

Composition and reactivity of coal from the Khoot deposit in Mongolia

The composition and reactivity characteristics of Khoot coal from Mongolia in the processes of pyrolysis, gasification, thermal dissolution, and the production of porous materials were determined. It was established that the coal is characterized by high activity in the reactions of destruction. In the process of semicoking, the yield of liquid tar was as high as 10%. Highly porous activated carbons with specific surface areas to 900 m²/g and high sorption capacities were obtained by the steam activation of carbonizates. To 60.8% liquid products at low gas formation can be obtained from the Khoot coal in the process of thermal dissolution in a hydrogen-donor solvent at 450°C without the use of hydrogen.     

Mixing State of Black Carbon Aerosol in a Heavily Polluted Urban Area of China: Implications for Light Absorption Enhancement

Black carbon (BC) is important for climate forcing, and its effects on the Earth's radiative balance remain a major uncertainty in climate models. In this study, we investigated the mixing state of refractory black carbon (rBC) and aerosol optical properties in a polluted atmosphere at Xi’an, western China. The average rBC mass concentration was 9.9 μg m^?3 during polluted periods, 7.6 times higher than that in clean periods. About 48.6% of the rBC was internally-mixed or coated with nonrefractory materials during polluted periods; this was 27% higher than in clean periods. Correlation analysis between the number fraction of thickly-coated rBC particles (f_BC) and the major particulate species indicate that organics may be the primary contributor to rBC coatings during polluted periods. The average mass absorption cross section of rBC (MAC_BC) particles at λ = 870 nm was 7.6 ± 0.02 m² g^?1 for the entire campaign. The MAC_BC showed a positive correlation with f_BC, and the enhancement of MAC_BC due to internal mixing was 1.8 times. These observations suggest that an enhancement of BC absorption by a factor of ～2 could be appropriate for climate models associated with high PM_2.5 levels.

Copyright 2014 American Association for Aerosol Research     

Low-temperature gasification of a woody biomass under a nickel-loaded brown coal char

Catalytic gasification of a woody biomass, Japanese cypress, was investigated under a prepared nickel-loaded brown coal (LY-Ni) char in a two-stage fixed-bed reactor. The nickel-loaded brown coal was prepared by ion-exchange method with a nickel loading rate of 8.3 wt.%. Nickel species dispersed well in the brown coal, and the LY-Ni char via devolatilization at 600 °C showed a great porous property with a specific surface area of 382 m² g^− 1.The LY-Ni char was confirmed to be quite active for the Japanese cypress volatiles gasification at a relatively low-temperature range from 450 to 650 °C. For example, at 550 °C, 16.6 times hydrogen gas and 6.3 times total gases were yielded from the catalytic steam gasification of Japanese cypress volatiles under the LY-Ni char, compared with the case of non-catalyst. The biomass tar decomposition showed a dependence on catalyst temperatures. When the catalyst temperature was higher than 500 °C, Japanese cypress tar converted much efficiently, high gas yields and high carbon balances were obtained.     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

Attrition of Victorian brown coal during drying in a fluidized bed

Analyzing the attrition of Victorian brown coal during air and steam fluidized bed drying, the change in particle size distribution over a range of initial moisture contents (60% to 0%) and residence times (0 to 60 minutes) was determined. Dried at a temperature of 130°C with a fluidization velocity 0.55 m/s and an initial particle size of 0.5–1.2 mm, both fluidization mediums show a shift in the particle size distribution between three and four minutes of fluidization, with a decrease in mean particle size from 665 µm to around 560 µm. Using differential scanning calorimetry (DSC), the change in particle size has been attributed to the transition between bulk and non-freezable water (approximately 55% moisture loss) and can be linked to the removal of adhesion water, but not to fluidization effects. This is proved through the comparison of air fluidized bed drying, steam fluidized bed drying, and fixed bed drying—the fixed bed drying is being used to determine the particle size distribution as a function of drying. The results show the three drying methods produce similar particle size distributions, indicating that both fluidization and fluidization medium have no impact upon the particle size distribution at short residence times around ten minutes. The cumulative particle size distribution for air and steam fluidized bed dried coal has been modeled using the equation P_d = A₂ + (A₁ ? A₂)/(1 + (d/x₀)^p), with the resultant equations predicting the effects of moisture content on the particle size distribution. Analyzing the effect of longer residence times of 30 and 60 minutes, the particle size distribution for steam fluidized bed dried coal remains the same, while air fluidized bed dried coal has a greater proportion of smaller particles.     

Higher Alcohol Synthesis Using K-Doped CoRhMoS2/MWCNT Catalysts: Influence of Pelletization,Particle Size and Incorporation of Binders

In this study, alkalinized MWCNT supported MoS₂ catalysts have been doubly-promoted with Co and Rh. Catalysts were prepared by the conventional co-impregnation method and stabilized under argon atmosphere. Characterization of the oxidic samples by BET revealed that the mesoporosity of the pristine MWCNT support was not compromised after loading a combined total of 30 wt% metals (9 wt% K, 4.5 wt% Co, 1.5 wt% Rh, and 15 wt% Mo) on the support; however, a significant decrease in specific surface area was observed. Broad angle XRD analysis confirmed the homogenous dispersion of catalyst metals on the support. Two catalyst grain sizes were first investigated to elucidate the effect of particle size: a finely ground powder (88 μm) and a pelletized form (1,780 μm). Despite the total alcohol yield of 0.261 g/(g_cat h) observed by conducting higher alcohol synthesis reaction at T = 330 °C, P = 8.3 MPa, H₂/CO = 1.25, and GHSV = 3.6 m _STP ³ /(kg_cat h) for the fine powdered sample, the relatively higher pressure drop could be minimized by using the pelletized form of the catalyst. Finally, a systematic study of variety of selected binders was conducted to gain insight of catalyst’s applicability for industrial purposes. Three selected binders namely: bentonite clay, coal tar, and humic acid were thus investigated; taking into consideration significant factors such as melting point and binder requirement per catalyst support. The CO conversions evaluated for the two binder-free catalysts (88 and 1,700 μm) showed that the catalyst with fine particle sizes (88 μm) performed better than that in the pelletized form (binder-free, 1,700 μm); yielding a maximum ethanol selectivity of 38.5 % at steady-state reaction conditions.     

Carbonization of coal pitch with graphite additives

The influence of added pyrolytic graphite and graphite foam on the crystalline structure of the product formed in the carbonization of moderate-temperature coal pitch at 900°C is investigated by X-ray diffraction analysis. All the additives catalyze the formation of graphite structures in pitch carbonization. However, no direct dependence of the catalytic efficiency on the structure of the carbon additive or its specific surface is observed. In the presence of graphite additives with a specific surface of 4–12 m²/g, more than 20% of a crystalline fraction is formed in the carbonization of pitch. This fraction is highly ordered, with large crystallites. On adding graphite foam, with a high specific surface (110 m²/g) and low packing density (4 g/L), the formation of graphite structures on pitch carbonization is less effective.     

Flash pyrolysis of coals: comparison of results from 1 g h−1 and 20 kg h−1 reactors

The performances of 1 g h^?1 and 20 kg h^?1 flash pyrolysers are compared for three Australian coals: Loy Yang brown coal (Victoria), Liddell bituminous coal (New South Wales), and Millmerran sub-bituminous coal (Queensland). The two reactors gave comparable yields of tar, char and C₁–C₃ hydrocarbon gases over a range of operating conditions for each particular coal. The yield of total volatile matter from Millmerran coal was similar from both reactors, as were the compositions of chars from Loy Yang coal and tars from the Liddell and Millmerran coals. For Millmerran coal, the yields of tar, C₁–C₃ gases and volatiles from the large reactor below 650 °C, were slightly lower than for the small reactor, possibly owing to a shorter retention time of Millmerran coal particles in the large-scale reactor. At a temperature near 600 °C tar yields were independent of tar concentration in the effluent gas, over a range 0.0025–0.1 kg m^?3 for Liddell coal, 0.005–0.26 kg m^?3 for Millmerran coal and 0.0045–0.09 kg m^?3 for Loy Yang coal. The tar yields from Millmerran and Liddell coals at 600 °C in the large reactor, correlate directly with the atomic $\text{H}\text{C}$ ratio of the parent coal, in the same manner as that found for a wider range of bituminous coals in the small-scale reactor.     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template

Mesoporous carbons (MCs) for supercapacitors were prepared from coal tar pitch by a microwave-assisted one-step process coupling the potassium hydroxide (KOH) activation and magnesium oxide (MgO) template. MCs were characterized by scanning electron microscope and X-ray diffraction. The results show that the specific surface area (S_BET), micropore volume and specific capacitance of MCs made by microwave heating as well as the energy density of MC capacitors pass through a maximum with increasing mass of MgO and the relative mass ratio of KOH/pitch. The S_BET of MCs varies from 1003 to 1394 m²/g. The S_BET and total pore volume of MC and microporous carbon made by microwave heating are bigger than that made by conventional heating. Under optimum conditions with the masses of coal tar pitch, MgO, KOH at 9 g, 12 g, 6 g, and the microwave power at 600 W, MC (MC_9-12-6) made at 30 min heating time shows a high specific capacitance of 224 F/g in 6 M KOH aqueous electrolyte after 1000 cycles. The results have shown that microwave-assisted rapid KOH activation coupled with the MgO template is an efficient one-step approach to the preparation of low cost yet high performance MCs for supercapacitors.