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The main objective of a series of our researches is to develop a novel acoustic-based method for activation of biochar. This study investigates the capability of biochar in adsorbing Ni(II) as a hazardous contaminant and aims at enhancing its adsorption capacity by the addition of extra nitrogen and most probably phosphorous and oxygen containing sites using an ultrasono-chemical modification mechanism. To reach this objective, biochar physically modified by low-frequency ultrasound waves (USB) was chemically treated by phosphoric acid (H3PO4) and then functionalized by urea (CO(NH2)2). Cavitation induced by ultrasound waves exfoliates and breaks apart the regular shape of graphitic oxide layers of biochar, cleans smooth surfaces, and increases the porosity and permeability of biochar’s carbonaceous structure. These phenomena synergistically combined with urea functionalization to attach the amine groups onto the biochar surface and remarkably increased the adsorption of Ni(II). It was found that the modified biochar could remove > 99% of 100 mg Ni(II)/L in only six hours, while the raw biochar removed only 73.5% of Ni(II) in twelve hours. It should be noted that physical treatment of biochar with ultrasound energy, which can be applied at room temperature for a very short duration, followed by chemical functionalization is an economical and efficient method of biochar modification compared with traditional methods, which are usually applied in a very severe temperature (>873 K) for a long duration. Such modified biochars can help protect human health from metal-ion corrosion of degrading piping in cities with aging infrastructure.

The present study discusses a novel biochar activation technique consisting of physical modification using low frequency ultrasound and chemical functionalization with individual amines and their b...

The objectives of a series of our researches are to determine the feasibility of applying ultrasonic pretreatment prior to biochar gasification. As per the initial results, the heating value (HV) of biochar significantly increased after acoustic treatment in water with dissolved CO2 (AIChE Journal, 2014;60:1054–1065). Accordingly, emphasis of the current work is placed on the parameters governing the HV of biochar in the early stage of the treatment. Switchgrass and miscanthus biochars were treated under different conditions. The reactant ratio, biochar:water:CO2, exhibited profound impacts on the synergism. The highest (but not yet systematically optimized) ratio of HV increase (or HV Gain, HG) to ultrasound energy supplied (ES) takes place when biochar-to-water ratio, or BC:W, equals 0.06 g/ml. The observed HG/ES is about 10, suggesting that the energy consumption is only a fraction of the acoustic energy supplied. Miscanthus biochar’s HV increases by up to 4.6% after treatment at 5% amplitude for 135 s (HG = 33 cal/g). For the same run, miscanthus biochar's H content increased by 42.7%. Changes in HV can be mediated by mineral leaching, C or H fixation, or O content loss. Mineral leaching is influenced by pH and CO2 concentration. CO2 and water are the sole contributors to C and H gains, respectively. CO2 concentration in the solution during the treatment is also affected by mass transfer limitations, ultrasound power, and design of the three-phase reactor. Increasing the BC:W ratio initially enhances the cavitation nuclei on the fluid/solid surface, and therefore sonolysis. The subsequent decrease in HV with increasing BC:W may be due to the limitation in ultrasound penetration and H supply from water. Carbon and hydrogen fixation may be connected to the formation of H2, CO, formic acid, formaldehyde, and associated radicals during sonolysis of aqueous CO2.

Generation of hydroxyl radicals (⋅OH) is the basis of advanced oxidation process (AOP). This study investigates the catalytic activity of microporous carbonaceous structure for in-situ generation of ⋅OH radicals. Biochar (BC) was selected as a representative of carbon materials with a graphitic structure. The work aims at assessing the impact of BC structure on the activation of H2O2, the reinforcement of the persistent free radicals (PFRs) in BC using heavy metal complexes, and the subsequent AOP. Accordingly, three different biochars (raw, chemically- and physiochemically-activated BCs) were used for adsorption of two metal ions (nickel and lead) and the degradation of phenol (100 mg/L) through AOP. The results demonstrated four outcomes: (1) The structure of carbon material, the identity and the quantity of the metal complexes in the structure play the key roles in the AOP process. (2) the quantity of PFRs on BC significantly increased (by 200%) with structural activation and metal loading. (3) Though the Pb-loaded BC contained a larger quantity of PFRs, Ni-loaded BC exhibited a higher catalytic activity. (4) The degradation efficiency values for phenol by modified biochar in the presence of H2O2 was 80.3%, while the removal efficiency was found to be 17% and 22% in the two control tests, with H2O2 (no BC) and with BC (no H2O2), respectively. Overall, the work proposes a new approach for dual applications of carbonaceous structures; adsorption of metal ions and treatment of organic contaminants through in-situ chemical oxidation (ISCO).

Renewable energy sources e.g. biofuels, are the focus of this century. Economically and environmental friendly production of such energies are the challenges that limit their usages. Microalgae is one of the most promising renewable feedstocks. However, economical production of microalgae lipid in large scales is conditioned by increasing the lipid content of potential strains without losing their growth rate or by enhancing both simultaneously. Major effort and advances in this area can be made through the environmental stresses. However, such stresses not only affect the lipid content and species growth (biomass productivity) but also lipid composition. This study provides a comprehensive review on lipid enhancement strategies through environmental stresses and the synergistic or antagonistic effects of those parameters on biomass productivity and the lipid composition. This study contains two main parts. In the first part, the cellular structure, taxonomic groups, lipid accumulation and lipid compositions of the most potential species for lipid production are investigated. In the second part, the effects of nitrogen deprivation, phosphorus deprivation, salinity stress, carbon source, metal ions, pH, temperature as the most important and applicable environmental parameters on lipid content, biomass productivity/growth rate and lipid composition are investigated.

A series of biochars were prepared from rice(RI), tobacco(TO), corn(CO), wheat(WH), millet(MI), and black bean straw(BB). These biochars were used to study the mechanism of elemental mercury(Hg0) adsorption by hydrochloric acid modified biochars. The biochars were modified by 1 M hydrochloric acid (HCl) and then used in a fixed-bed Hg0 adsorption experiment. As would be expected, the results indicated that HCl modification increased the Hg0 adsorption performance of the six biochars. After modification, the Hg0 adsorption efficiency of tobacco biochar increased from 8.2% to 100.0%, and the average Hg0 adsorption capacity of the biochars increased by 61 times. The acid modification dissolved the metal compounds in the biochar, reducing the metal content and increasing the average surface area of the biochar. The average surface area of the raw biochars increased from 29.9 to 110.1 m2/g after HCl modification. The extra surface area was mostly created in the micropores, leading to a significant increase in the amount of micropores. These micropores effectively adsorbed the Cl atoms, which acted as active sites for Hg0. In the adsorption process, Hg0 diffused into the interior of modified biochars via mesopores, and finally the adsorbed Cl in the micropores reacted with Hg0 to form HgCl2.

This paper describes a two-stage biochar activation process for CO2 capture, which includes acoustic treatment and amination. Contrarily to traditional carbon activation at temperatures above 700 °C, both stages of the current process are conducted at or near room temperature. It is known that CO2 can be fixed on the edge carbons of polycyclic aromatics hydrocarbons (PAHs) through thermal and reductive photo-carboxylation. Our previous work on biochar suggested that carbon of CO2 could be chemically fixed on biochar through acoustic or photochemical treatment of biochar in water/CO2 systems under ambient conditions. Separately, the graphene oxide (GO) literature reveals that carboxylic acids, epoxy and hydroxyl groups on biochar surface often serve as the active sites for converting GO to a new family of chemicals; amines are commonly grafted on these groups in the functionalization. Biochar has graphite and graphitic oxide clusters that consist of the oxygen functional groups mentioned above. These oxygen functionalities can be utilized for CO2 adsorption when functionalized with amine. Thus, the present study focuses on maximizing the CO2 capture capacity by manipulating the physicochemical structure of a pinewood-derived biochar. In this two-stage process, 30 s sonication at ambient temperature was applied to physically activate biochar prior to functionalization. Low-frequency ultrasound irradiation exfoliates and breaks apart the irregular graphitic layers of biochar, and creates new/opens the blocked microspores, thus enhancing the biochar’s porosity and permeability that are the keys in functionalization and subsequent CO2 capture. The sono-modified biochar was then functionalized with tetraethylenepentamine (TEPA) in the presence of two activating agents. The changes in surface characteristics, functional groups, graphene-like structure, and functionalization using activating agents were examined in detail and the capacity of the final products in CO2 removal was tested. The experimental results revealed that CO2 capture capacity, from a flow containing 10 and 15 vol% CO2, was almost 7 and 9 times higher, respectively, for ultrasound-treated amine-activated biochar, compared to raw biochar. The optimum capacity was 2.79 mmol/g at 70 °C and 0.15 atm CO2 partial pressure. Cyclic adsorption and desorption tests revealed that the CO2 capture capacity decreased 44% after 15 cycles.

Biochar, known as a byproduct of biomass pyrolysis, was prepared from rice straw (R6), tobacco straw (T6), corn straw (C6), wheat straw (W6), millet straw (M6), and black bean straw (B6) in high purity nitrogen at 600 °C. Chlorine (Cl) non-thermal plasma was used to increase Cl active sites on biochar to promote the mercury removal efficiency. The physio-chemical properties of biochar were characterized by proximate analysis, ultimate analysis, BET, SEM, TGA, FTIR, and XPS. Modification by chlorine plasma increased the Hg0 removal efficiency of the biochar from around 8.0% to 80.0%. The Hg0 adsorption capacity of T6 was 36 times higher after Cl2 plasma modification. Plasma caused the biochar surface to become porous and promoted the thermal stability of the biochar. Sulfur (S) content remained in the range of 0.5–0.7%, elemental/organic sulfur and sulfide were converted to sulfate during plasma treatment. The relative intensity of the oxygen functional groups (C O, C O and C(O) O C) were enhanced, while the content of oxygen (O) in biochar decreased. The main reason for the improved mercury removal efficiency by modified biochars was attributed to the increased number of C Cl groups on the surface of the biochars induced by Cl2 plasma. The C Cl groups functioned as activated sites and promoted the Hg0 removal efficiency.

We report results of theoretical evaluation of the mechanisms of possible radical reactions on the edge-site of biochar with CO 2 · - , OH , and H in irradiated aqueous solution. The computational studies were performed for model poly aromatic systems. Obtained mechanisms reflect one of the routes of the oxygen loss accompanied by increase of hydrogen content, as observed in photochemical experiment. The reaction of CO 2 · - with the edge site of biochar mainly leads to reduced rather than oxidized products. The mechanism of CO2 capturing is mapped by different routes of one-electron reduction and radical addition to the aromatic ring.

Biochar was subjected to N2-plasma treatment after adsorbing water or oxygen. The mercury removal efficiency of the obtained samples was tested. The results of H2O-thermogravimetric and O2-temperature programmed desorption show that biochar had adsorption capacity for both water and oxygen during storage. The adsorbed water exhibited an inhibitory effect on mercury removal. However, after plasma treatment, water decomposed into oxygen-containing active radicals and combined with biochar to form oxygen-containing functional groups. The generated functional groups compensated for the inhibition of mercury capture. After the biochar adsorbed oxygen, the biochar was easily sintered under plasma, thereby reducing the mercury removal performance. The oxygen-containing functional groups formed by plasma treatment of oxygen adsorbed biochar also improved the mercury removal efficiency. Hg-temperature programmed desorption revealed that Hg0 could be oxidised by the generated oxygen-containing functional group to form HgO. Correlation analysis showed that the oxygen adsorbed by the biochar from air during storage was the main source of oxygen-containing functional groups generated under a non-oxygen plasma environment. The correlation coefficient was up to 0.999. During normal storage, the oxygen adsorbed by the adsorbent from the air can be converted into oxygen-containing functional groups during the plasma modification process, thereby oxidising Hg0.

Conventional carbon activation requires heating carbon at a temperature greater than 700 °C for over 3 h, consuming 18,600 kcal/kg of activated biochar. In contrast, the ultrasound treatment method is conducted at ambient condition for a very short duration (∼30 s, which requires about 1135 kcal/kg of activated BC produced. The advanced low-temperature acoustic-based surface modification method not only increases the porosity and surface functionality of raw biochar, but also is economically feasible and environmentally friendly. As a sequel of our previous works, this study aims to investigate the interaction between ultrasonic-structural modification with four different pre-treatments including i) control with no pretreatment, ii) EDC/HBOt, iii) alkali using KOH, iv) acid using HNO3 or H3PO4. The process was then followed by amine functionalization with DEA (diethanolamine) for nickel removal. The results demonstrated that all acoustic-based amine-functionalized biochar samples, without any exception, had more amine- and oxygen-containing functional groups as well as micro porosity, compared to those aminated without acoustic-activation, particularly in samples pretreated with HNO3 and H3PO4. Despite an increase in porosity by ultrasonication, metal leaching from US-only samples and those activated with EDC/HOBt was observed during longer adsorption durations. However, the synergism created by the combined effect of ultrasound and KOH and H3PO4, not only enhanced the adsorption capacity of biochar but also significantly reduced the adsorption duration from 8 to 3 h. The highest nickel adsorptions were observed for ultrasonic-amine samples activated with H3PO4 > HNO3 ∼ KOH, which were far higher (60 %, 49 %, and 46 % more adsorption, without any leaching) than raw or US-biochar, or biochar aminated with EDC/HOBt or without pretreatment.

A critical literature review suggests that carbonaceous compounds react with (CO2 +H2O) mixture through thermal, photochemical, and sonochemical/sonophysical routes. A biochar was selected for studying these effects at 60°C and 1 atm for its potential benefits on power generation and CO2 capture. All treatments remove sizable minerals (K, Na, and Si) detrimental in power generation, and introduce carbon (up to 16% of original carbon in biochar) into the biochar matrix. Most treatments show increased hydrogen (up to 24%). Treatments lead to notable increased heating value of biochar (up to 50%). Treated biochars show increase (up to 19 fold) in internal surface area. The ultrasound energy output is a fraction of the increased heating value. Thus, pretreatment is potentially attractive for increasing the energy efficiency in combustion and gasification. Moreover, better understandings of the salient reactions of these processes will be advantageous for the development of advanced adsorbents for CO2 capture. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1054–1065, 2014

This work demonstrates that biomass fly ash, a carbon-containing by-product of a commercial pine-bark fired grate boilers, is a more viable and effective NO reducing agent than lignite char in a gasstream containing NO, O 2 and He in a tubular reactor at 300 to 600 °C that simulates the post-combustion zones. It requires no chemical or physical activation. It seems to follow the reburning mechanisms reported earlier. CO is a pivotal reaction intermediate. Alkali and alkaline earth metals catalyze both carbon oxidation leading to CO formation, and oxygen tranfer leading to CO scavenging of surfaceoxides formed after adsorption of NO. Empirical rate expressions for carbon oxidation and NO reduction are developed. The following rate model is used to recover the rate constants of carbon oxidation in the simulated flue gas. d X d t = k ( 1 − X ) ( P oxygen ) m A exp( − k c h a r d e a c t i v a t i o n t ) where X , t , k , P oxygen , m , A and k char deactivation denote carbon conversion, reaction time, rate constant based on per unit surface area, partial pressure of O 2 at the inlet, reaction order, N 2 BET surface area per unit weight of the sample, and rate of carbon deactivation, respectively. A first-order rate expression is adopted for recovering the rate constants of NO reduction.

Polar solvents are known to swell coal, break hydrogen bonds in the macromolecular structure, and enhance coal liquefaction efficiencies. The effects of the pretreatment of coal using supercritical CO{sub 2} on its physical structure and combustion properties have been studied at the bench-scale level. Emphasis has been placed on NO reburning, NO emissions during air-fired and oxy-fired combustion, and loss on ignition (LOI). Pretreatment was found to increase porosity and to significantly alter the fuel nitrogen reaction pathways. Consequently, NO reduction during reburning using bituminous coal increased, and NO emissions during oxidation of lignite decreased. These two benefits were achieved without negative impacts on LOI.

It is known that polar solvents swell coal, break hydrogen-bonds in the macromolecular structure, and enhance coal liquefaction efficiencies. The effects of drying, interaction with supercritical CO2 and degassing on the physical structure of coal have been studied using gas sorption technique and a scanning electron microscope (SEM). Both drying and interaction with supercritical CO2 drastically change the micropore and mesopore surface area, absolute volume, and volume distribution in both bituminous coal and lignite. Degassing removes debris in the pore space which allows for better analysis of the changes in the morphology that were induced by drying and exposure to supercritical CO2. SEM reveals that interaction of bituminous coal with supercritical CO2 results in an abundance of carbon structures similar to the maceral collinite.

In a recent study, we discovered that oxygen from the gas phase, organic portions of the coal, and minerals in the coal have profound influence on the formation and desorption of stable surface oxides in the early stages of coal combustion. In an attempt to isolate the effects of minerals, demineralized coals (DMC) are oxidized in O{sub 2} with a contact time less than 1 s, and the amount and strength of stable surface oxides are characterized by temperature-programmed desorption (TPD) up to 1650{sup o}C. Young chars derived from both demineralized lignite and bituminous coals show low and flat TPD profiles over a wide temperature range, signifying the minerals' catalytic activities in forming stable surface oxides for both coals. Indeed, the oxidation rates of chars from both bituminous coals and lignite, estimated based on the O{sub 2} concentrations entering and exiting the Al{sub 2}O{sub 3} reactor, were higher than their DMC counterparts. Moreover, graphite, containing no minerals and organically bound oxygen, has an even lower oxidation rate. Similar to those for the raw coals, the combined oxygen balance and elemental analysis of chars from DMC suggests that the oxygen in the organic portion of the lignite activates oxygen turnover andmore » carbon oxidation during its combustion; neither chars from raw nor demineralized bituminous coals possess these properties. X-ray photoelectron spectroscopy (XPS) of raw and demineralized bituminous coals and their char show peaks at around 532.0 eV in the O(1s) difference spectrum, suggesting the possible existence of intercalated stable surface oxides. 35 refs., 7 figs., 4 tabs.« less

To obtain representative temperature-programmed desorption (TPD) profiles of young oxidized chars up to 1650 °C with minimal reactor wall interferences, the chemistry and physics of four ceramic materials has been critically reviewed. A two-staged experimental apparatus is then uniquely designed to produce chars in an Al2O3 flow reactor with 1−21% O2 followed by in situ TPD with a SiC tube. Comparison of TPD profiles of oxidized chars with those from pyrolyzed chars and ashes suggests early-stage char oxidation is profoundly influenced by oxygen from three sources: organics oxygen, mineral matters, and gas phase O2. Young chars oxidized at 1000 °C with less than 0.3 s residence time shows CO desorption peaks during TPD at three distinct temperatures: 730, 1280, and 1560 °C. The peaks at 730 °C are mainly caused by incomplete devolatilization. The peaks at 1280 °C mainly represent desorption of stable surface oxides and incomplete devolatilization. Increasing the gas phase oxidants notably increases the am...

This paper reports our first study on the deactivation of young chars in flame conditions. The quantity and strength of surface oxides on young chars are monitored in situ by temperature-programmed desorption (TPD) up to 1700 °C. Young chars contain more abundant surface oxides than old chars over a wide range of temperature. Lignite chars possess more oxides than chars derived from a bituminous coal. Chars oxidized at 629 °C show desoprtion products at three distinct temperatures: 725, 1430, and 1700 °C. The TPD peaks around 725 °C correspond to activation energies in the range of 107-170 kJ/mol and have been well-documented in the literature. CO desorbed at around 1430 °C corresponds to activation energies over 300 kJ/mol, signifying the possible roles of strongly bound oxides on the basal planes of carbon. Search of the oxygen source for the huge amount of CO production at 1700 °C reveals that commonly adopted alumina tubes and support materials decompose to Al 2 O (g) and emit a notable amount of O 2 at temperatures above 1300 °C. Moreover, alumina tube and support materials react with CO and form CO 2 ; they also react with carbon and form CO and aluminum oxycarbides. SiC tube, on the other hand, is oxidized by O 2 , CO 2 , and H 2 O and forms SiO (g) , SiO 2(s) , Si-(OH) 4(g) , and CO above 650 °C. Moreover, Si can also form through a secondary reaction of SiC and SiO 2 . Thus, alumina appears suitable for the oxidation part of the experiments, where up to 120 ppm of O 2 emission is acceptable at a temperature of 1700 °C. SiC appears acceptable for TPD, though a small amount of SiC may be oxidized by the TPD product, CO 2, at temperatures above 900 °C. Oxidation of SiC prior to TPD should be avoided.

Isotopically labeled N15O was used to study the interaction of fuel nitrogen from coal with NO in a simulated reburning environment. Experiments were conducted in an alumina flow reactor operated at 1100°C with a reaction time estimated at 0.2 s. A North Dakota lignite and a Pittsburgh #8 bituminous coal were burned with a simulated flue gas containing 1000 ppm of N15O. Stoichiometric ratios ranged from 0.7 to 1.0. Species and isotope separation were accomplished using GC/MS. The ratio of labeled to unlabeled isotopes of each major nitrogen-containing species varied with stoichiometry, but not with coal type. Delayed nitrogen evolution from both coals was evident from the data. Data analysis showed that significant N2 production (i.e., greater than 50%) probably occurred through non-NO pathways. Little N15O was observed, indicating low conversion rates of intermediates to NO after significant nitrogen evolved from the coal.

Desulfurization removes elemental sulfur and its compounds from solids, liquids, and gases. Predominantly, desulfurization involves the removal of sulfur oxides from flue gases, compounds of sulfur in petroleum refining, and pyritic sulfur in coal cleaning. This chapter discusses the following topics: 1. Sulfur pollution (sulfur oxides, hydrogen sulfide, and organic sulfur pollutants). 2. The US Air Quality Act. 3. Solid-phase desulfurization (coal cleaning, gasification, and liquefaction). 4. Liquid-phase desulfurization (acid-lake restoration for H2SO4 removal and groundwater decontamination for H2S removal). 5. Gas-phase desulfurization (SO x and H2S removals from air emission streams).

The investigation of this quarter focuses on the rates of NO reactions with chars in various gaseous environments. The results have revealed significant insights into the NO reduction mechanisms on char surface, particularly when the oxidants, O{sub 2} and CO{sub 2}, are introduced into the feed. Indeed, evidences suggest that the formation of stable oxygen complexes is the major cause of differences in NO reactivity on chars of different origins. The oxidants retard the reactivity of char derived fro the bituminous coal more seriously than they affect the char derived from lignite. Furthermore, additions of these oxidants into the reacting stream produce additional yields of CO and CO{sub 2} during NO reaction with lignite char, suggesting gasification of carbon from lignite char. No excess CO and CO{sub 2} were observed when the bituminous coal char was used. These yields of CO and CO{sub 2} also imply that desorption of stable surface oxygen complex is a rate-limiting step which may be catalyzed by the mineral matters during reactions involving lignite char. Surface area evaluated by CO{sub 2} and Dubinin-Radushkevich (D-R) equation is not a normalization factor of char reactivity during reburning. In the absence of oxidants, the bituminous coal char shows drastic increase in activation energy at about 950 {degrees}C indicating transition of desorption to adsorption controlled mechanisms. When CO{sub 2} is introduced, the transition temperature increases. When oxygen is also added, no such transition is observed up to 1100 {degrees}C. Lignite char reactivity increases smoothly over the temperature range 800 to 1100 {degrees}C. It is also observed that char reactivity decreases with increasing pyrolysis temperature which may be caused by closure of pores due to graphitization. The rate of NO reduction on the Pittsburgh {number_sign}8 coal char is then in good accord with that of a West Virginia coal char reported by De Soete (1980).

The progress in this quarter includes four parts. In the first segment, the implications of our data reported in the List quarter are discussed further. BET N{sub 2} surface area does not seems to be the only contributing factor to the remarkable activity of lignite char during reburning, and chars of different origins probably have different controlling steps in the overall surface reaction mechanisms. Unlike NO reduction in the gas phase, oxygen inhibits the heterogeneous mechanisms. The second part of this report justifies the use of our laminar flow reactor system for the measurement of reaction rate. Dispersion model is used in the analysis. An expression relating the rate constant with the experimentally obtainable NO conversion for our flow reactor have been derived. Rates of NO/char reaction for six series of experiments have been measured over the temperature range 800 to 1100{degrees}C. These six series of experiments have been conducted with two different chars, one bituminous coal char and one lignite char, and three different levels of feed NO concentrations, 200, 400 and 1000 ppm. Results from the comparison of char activities suggest that, in the absence of O{sub 2} and CO{sub 2}, the origin of char is not a significant factor for NO reduction. The CO/CO{sub 2} ratio in the products is higher than one under all test conditions, but the ratio increases with increasing feed NO concentrations. Recoveries of oxygen form the lignite char at temperatures above 1050{degrees}C is higher than 1 indicating gasification of organic oxygen in the char. Surface areas of selected chars after devolatilization and after reburning have been analyzed by BET in N{sub 2}. Results indicated char surface area changes after reburning, which is caused either by the higher temperature of reburning or by surface reaction.

The susceptibility of a group of US coals to the production of light gaseous and liquid hydrocarbons during flash hydrogenation is examined. Eight coals ranging from lignite to high-volatile A bituminous and representing five provinces, have been flash heated in 101.3 MPa of flowing hydrogen using a bench scale reactor. A 0.6 s gas phase residence time was provided to hydrocrack the vapour products. Temperatures ranged from 750 to 850°C, where maximum yields of ethane and BTX (benzene+toluene + xylene) are found. The carbon conversion decreased with increasing rank at fixed reaction conditions. Methane yields are highest for lignite. Peak ethane yields range from 6.4 to 9% carbon conversion. BTX yields have a shallow maximum at intermediate ranks, decreasing towards high and low rank coals. Total liquid yields range from 14 to 43%. Although a definite variation of yield with rank is evident, the trends, especially total liquid yields, are attended by considerable scatter. Rank is not the only, and indeed may not be the most significant variable in determining the yield of individual species in flash hydrogenation. To establish the significant variables a stepwise regression procedure was applied to the experimental data using information from the elemental, proximate and petrographic compositions of the coals as independent variables. Two variables are adequate in all cases to correlate species yield and coal properties. Exinite appears to be capable of increasing the amount of liquid obtained from other macerals.

An interesting correlation has been observed between the volatile yield for three coal conversion processes and the oxygen and aliphatic hydrogen (Hal) content of the coal. The three processes are: (1) rapid pyrolysis in vacuum, (2) hydropyrolysis at ≈10 MPa hydrogen, and (3) liquefaction with tetralin at 400 °C. The volatile yield for the first two processes and for low sulphur coals studied in the third process may be predicted with the equation: Yield≈0.8 OT+15 Hal where: OT, the organic oxygen concentration measured by ultimate analysis; and Hal is the aliphatic hydrogen concentration determined from Fourier Transform infrared (FTIR) measurements. The similarity of yields for these processes suggests that they are basically controlled by thermal decomposition. Justification for the above equation is offered by considering a recently developed model for thermal decomposition of coal. The correlation does not fit a group of high sulphur coals studied in the liquefaction programme. These coals have extremely high volatile yields which may be a result of catalytic activity.

This program addresses the mechanisms of NO reduction in pulverized coal flames using reburning. Using both thermodynamic and kinetic simulation combined with both pilot and bench scale experimental work, we propose to better define the conditions that lead to the destruction of NO, without the concomitant increase in other nitrogeneous pollutants. Specifically, the interactions between NO and hydrocarbon constituents in the fuel, and the fate of fuel nitrogen are the focal points of this research. Isotope doped 15 NO is used for tracing the reaction pathways.