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Yue Xu,1,* Weiyin Chen,1,* Zeran Chen,2 Mengyuan Huang,1 Fang Yang,1 Yang Zhang1 1Hospital of Chengdu University of Traditional Chinese Medicine, Chengdu, 610072, People’s Republic of China; 2School of Medical and Life Sciences, Chengdu University of Traditional Chinese Medicine, Chengdu Sichuan, 610041, People’s Republic of China*These authors contributed equally to this workCorrespondence: Fang YangHospital of Chengdu University of Traditional Chinese Medicine, No. 39 Shi-er-qiao Road, Chengdu, 610075, People’s Republic of ChinaTel/Fax +86 28- 87783481Email yfgreens2013@163.comYang ZhangHospital of Chengdu University of Traditional Chinese Medicine, Chengdu, 610072, People’s Republic of ChinaEmail zhangyang@cdutcm.edu.cnObjective: The traditional Chinese medicine (TCM) formulation Xiaoyao San (XYS) has a good clinical effect in treating ischemic stroke (IS). We explored the mechanism and material basis of XYS in IS treatment.Methods: Network pharmacology was used to construct a network of XYS components and IS targets. R software was used to analyze the biological process and pathway analysis of the targets of XYS in IS treatment. In vitro, a model of apoptosis of PC12 cells induced by oxygen-glucose deprivation/reperfusion (OGD/R) was established to evaluate the neuroprotective effect of XYS and its influence on the expression of apoptotic protein-related genes. The affinity between the potentially active compounds in XYS and apoptotic proteins was evaluated by molecular docking.Results: XYS was shown to have 136 chemical components that exert potential anti-IS activity by acting on 175 proteins. Bioinformatics analysis showed that apoptosis and the phosphoinositide 3-kinase/protein kinase B (PI3K-Akt) signaling pathway were the main signaling pathways of XYS. In vitro experiments showed that XYS could improve the effect of OGD/R on PC12-cell activity (EC50 = 0.43 mg/mL) and inhibit apoptosis. The main mechanisms were related to the improvement of oxidative stress and regulation of apoptosis-related gene expression. Molecular docking showed that C22, C102 and other components in XYS had a strong affinity with apoptosis-related proteins.Conclusion: Network pharmacology, in vitro experiments, and molecular docking were used, for the first time, to study the material basis and molecular mechanism of XYS in IS treatment from the perspective of multiple targets and multiple pathways. We provided a new approach for the future study of TCM formulations in the treatment of complex diseases.Keywords: apoptosis, neuroprotection, biological function, pharmacological mechanism

The present study investigates the impact of biomass origin on the properties of biochar and its interaction with different treatment conditions, CO2 adsorption, and regeneration ability. The bioch...

Purpose: To investigate the effect of Shenxiong Drop Pill (SXDP) on cerebral infarction (CI) in rats, and the involvement of anti-inflammatory response in the process.Methods: Rats were sacrificed at three different time points, viz, 24, 48 and 72 h after establishment of CI model. Neurological deficit score (NDS) was determined using Bederson’s neurological behavioral scoring method, whereas triphenyltetrazolium chloride (TTC) staining was used to show brain injury. The integrated optical density (IOD) of Nissl bodies and caspase-3-positive nerve cells were measured with Nissl staining and SP kit, respectively. The mRNA expression of intercellular adhesion molecule 1(ICAM-1) was determined using reverse transcription-polymerase chain reaction (RT-PCR).Results: SXDP produced neuroprotective effect at high, medium, and low doses. The infarct volumes in the high-, medium- and low-dose SXDP, and cyclophosphamide groups were significantly reduced at each time point. Different doses of SXDP significantly reduced the mRNA expression of ICAM-1 and the IOD of caspase-3.Conclusion: These results indicate that SXDP exerts neuroprotective effects against ischemic injury by negatively regulating ICAM-1/caspase-3 downstream of inflammatory and apoptosis pathways.

The present study discusses a novel ultrasound promoted amination technique to functionalize graphene oxide (GO) for CO2 adsorption. Graphene oxide was synthesized following the modified Hummer’s method. The developed functionalization technique integrates the advantages of low-frequency ultrasonic physical activation with the chemical functionalization using tetraethylenepentamine (TEPA). Acoustic treatment exfoliates the clusters of graphene oxide and enhances the surface area for the subsequent amine functionalization and CO2 adsorption. Changes in textural properties, surface functionalities, thermal stability, and elemental compositions were examined before and after activation of graphene oxide. The characterization results revealed substantial increment of N content, from 0.08 in pristine to 4.84% in functionalized GO and the subsequent reduction in surface area from 289 to 198 m2/g in the functionalized GO, indicating attachment of TEPA to GO structure. CO2 adsorption experiments were conducted under diluted CO2 with the partial pressure of 0.10 atm. at 338 K and the results revealed that ultrasonic-TEPA activated GO possessed enhanced adsorption capacity of 1.2 mmol g−1 over pristine GO. While pristine GO could only achieve the maximum adsorption capacity of 0.3 mmol g−1 at 303 K. Besides, the sonochemically modified adsorbent showed stable cyclic adsorption-regeneration performance with only 1% reduction in adsorption capacity after 10 cycles. Finally, the effectiveness of the developed physicochemical activation technique was determined by comparing its adsorption capacity with the adsorbents found from literature.

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.

This study investigates the potential of cow dung, an animal manure, as a binder to enhance the physicochemical properties of the base pellet (a mixture of wheat straw and rice husk). In the first step, preliminary experiments were performed to select the best composition of wheat straw and rice husk for the base pellet. The selection was based on calorific value. Subsequently, the effect of operating parameters such as varying compositions of cow dung (0–100%), molasses concentration (0–100%) and drying time (12–48 h) was investigated. Thus, Central Composite Design using Response Surface Methodology was used to investigate the proximate analysis, calorific value, bulk density and durability of biomass pellets. The experimental results suggested that the addition of cow dung into the base pellet resulted in the increase of volatile matter, ash content, bulk density and durability of the base pellet. As a result, the maximum calorific value of 14.98 MJ/kg, moisture content of 3.37%, volatile matter of 45.49%, ash content of 31.38%, bulk density of 108990 kg/m3 and durability of 95% were obtained. However, optimization of operating parameters was performed to optimize the ash percentage. With the pellet composition of 8.5% (base pellet composition of 90% wheat straw and 10% rice husk), molasses concentration of 50% and drying time of 12 h, 52% reduction in ash content and 2.3% increase in calorific value were obtained at the cost of 38% reduction in the bulk density and insignificant reduction in durability of the produced pellet. Therefore, the use of waste material like cow dung as a binder can be considered as a sustainable approach to improve the physicochemical properties especially durability of biomass pellets. Thus, it can effectively be used to fulfill the energy and heating requirement of rural areas.

The present study examined the effect of pyrolysis temperature on the physicochemical properties of biochar, activation process and carbon capture. Two different categories of biochars were synthesized from herbaceous (miscanthus and switchgrass) or agro-industrial (corn stover and sugarcane bagasse) feedstock under four different pyrolysis temperatures- 500, 600, 700 and 800 oC. The synthesized biochars underwent sono-amination activation comprising low-frequency acoustic treatment followed by amine functionalization to prepare adsorbents for CO2 capture. As per the elemental analysis, the elevated pyrolysis temperature resulted in increased %C and %ash contents and reduced %N contents of biochar. The textural analysis exhibited almost 3-times enhancement of micro surface area and pore volume upon increasing the pyrolysis temperature from 500 to 700 oC, though further increase to 800 oC reduced the micro-porosity and the surface area. The intermediate temperatures of 600 and 700 oC revealed the highest interactions with ultrasound-amination, which significantly intensified CO2 adsorption. Accordingly, the CO2 capture capacity of sono-aminated biochars synthesized at 600 and 700 oC were almost 200% greater than that of raw biochars. There were 127-159% and 115-151% increases in adsorption capacity of biochars synthesized at 800 and 500 oC upon ultrasono-amine functionalization. Miscanthus biochar synthesized at 700 oC and treated sono-chemically demonstrated the highest adsorption ability of 2.89 mmol/g at 70 oC and 0.10 atm partial pressure, which is 211% higher than its pristine condition. The superior adsorption capacity of miscanthus (at 700 oC) can be attributed to its large surface area (324.35 m2/g), high carbon content (84%), and low ash content (4.9%), as well as its %N content after sono-amination that was twice that of raw char.

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.

Biochar (BC) generated from thermal and hydrothermal cracking of biomass is a carbon-rich product with the microporous structure. The graphene-like structure of BC contains different chemical functional groups (e.g. phenolic, carboxylic, carbonylic, etc.), making it a very attractive tool for wastewater treatment, CO2 capture, toxic gas adsorption, soil amendment, supercapacitors, catalytic applications, etc. However, the carbonaceous and mineral structure of BC has a potential to accept more favorable functional groups and discard undesirable groups through different chemical processes. The current review aims at providing a comprehensive overview on different chemical modification mechanisms and exploring their effects on BC physicochemical properties, functionalities, and applications. To reach these objectives, the processes of oxidation (using either acidic or alkaline oxidizing agents), amination, sulfonation, metal oxide impregnation, and magnetization are investigated and compared. The nature of precursor materials, modification preparatory/conditions, and post-modification processes as the key factors which influence the final product properties are considered in detail; however, the focus is dedicated to the most common methods and those with technological importance.

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.

Primary particles emitted from fuel combustion mainly involve filterable particulate matter (FPM) and condensable particulate matter (CPM). Particularly, CPM has emerged as a subject for further emission control. This study investigated the effects of the sampling temperature and excess air coefficient (EAC) on the total mass, chemical speciation, and particle size distribution of CPM by integrating Electrical Low-Pressure Impactor+ (ELPI+) sampling devices with the EPA Method 202 (dry impinger method). The total mass of CPM increased with the sampling temperature and EAC. Specifically, the total concentration of CPM was 10.51–39.93 mg/m3, in which the mass fraction of organic species varied between 8.74 and 49.80%, and the organic components in CPM followed the ranking order of alkanes/alkenes (62.6–78.6%), oxygen-containing volatile organic compounds (OVOCs) (19.7–35.4%), and aromatics (5.6%). Compared with other inorganic species such as HCl and NOX, SO3 had a higher migration tendency from the flue gas to CPM. The particle size distribution suggested that heterogeneous condensation was responsible for the whole size range of particles in CPM, whereas the homogeneous condensation led to the increase of finer particles (smaller than 0.2 µm). Accordingly, adjusting the emission temperature and EAC could help to control the emission of CPM.

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.

Magnetization facilitates the separation and reuse of adsorbents, but significantly reduces the adsorption capacity. In this study, a double layer magnetized/functionalized biochar composite was synthesized through a hybrid post-pyrolysis magnetization which sustained and even significantly increased the adsorption capacity of microporous carbonaceous biochar (BC). The developed process included i) structural modification of biochar under ultrasound waves, ii) magnetization with magnetite (Fe3O4) nanoparticles, and iii) functionalization with 3-aminopropyltriethoxysilane (TES). Ultrasound irradiation exfoliates and breaks apart the irregular graphite layers of biochar, and creates new, or opens blocked, micropores, thus enhancing the BC’s porosity. For its part, TES stabilizes the magnetic nanoparticles on the biochar surface, while it participates in water decontamination through the strong chelation ability of its amino groups toward metal ions. Scanning electron microscopy demonstrated the stable and uniform distribution of Fe3O4 nanoparticles on the surface of microporous biochar, and Fourier-transform infrared spectroscopy indicated effective surface functionalization. In addition, although magnetization usually reduces the porosity of carbonaceous adsorbents, the ultraviolet–visible spectroscopic analysis showed that double layer magnetic biochar composite exhibited a much greater ability to remove Ni(II) and Pb(II), with 139 % and 38 % higher adsorptions than raw biochar. Almost complete removal of Pb (91 %) was observed by magnetic-BC and the adsorbent could easily be separated using a neodymium magnet. This high performance can be attributed to the synergistic effect of ultrasound activation on increasing the porosity and surface area of biochar along with enhanced chelation imparted by amine functionalization. The developed technique can be used for synthesizing advanced adsorbents for removal of nuclear waste-related metal ions from aqueous environments.

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

It is known that NO in the flue gas can be effectively converted to NO2 by O3. The objective of this work is to investigate the feasibility of simultaneously abating NO2 and SO2 from flue gas by liquid-phase conversion. A suite of cost-effective additives for enhancing NO2 absorption through enriching the concentration of sulfite ion, SIV, in the liquid phase has been evaluated under pH similar to traditional flue-gas desulfurization (FGD). Experiments were conducted in a lab-scale washing tower with CaSO3 slurry, including metal and non-metal additives: FeSO4, FeCl2, Fe2(SO4)3, MnSO4, MnCl2, MgSO4, MgCl2, (NH4)2SO4, and NH4Cl. All of these additives enhance the absorption efficiency of NO2. Ferrous sulfate, FeSO4, is the most effective additive, with absorption efficiency reaching 95%, but the loss of additive is high because of the oxidation of FeII into FeIII. Ammonium sulfate, (NH4)2SO4, has similar absorption efficiency but shows lower loss during absorption. Its absorption efficiency improves with a...

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.

Potential substitutes of natural gas and lignite fly ash as NO and HCN reducing agents, respectively, for heterogeneous reburning were examined in a bench-scale apparatus equipped with a simulated reburning and a burnout furnace. Selection of NO reducing agent is based on fuel volatility and nitrogen functionality. HCN reducing agent selection is based on literature data. A wide range of waste materials and industrial by-products show overall NO reduction efficiency up to 88% at reburning stoichiometric ratio 0.90 or 0.95. Mixed fuel containing scrap tire and Fe 2 O 3 is particularly effective. Though its cost is constrained by the energy-intensive operation of grinding the tire, the estimated raw-material cost is better than that of natural gas reburning and highly competitive against SCR. A first-level approximation study of the selectivities of nitrogen species to form NO in burnout zone reveals the importance of HCN and char nitrogen reaction mechanisms.

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.

Recent study of heterogeneous reburning suggests effective NO reduction requires an adequate carbon source and a pool of catalysts that reduces not only NO, but also the reaction intermediate HCN [Chen WY and Tang L. Variables, kinetics and mechanisms of heterogeneous reburning. AIChE J 2001;47:2781-2797]. The current work demonstrates that ashes from lignite-fired power plants contain these desirable catalytic ingredients. Their reactivity is slightly lower than that of ashes produced in laboratory at lower temperatures, probably due to the formation of crystalline structure. The current work also demonstrates that for the power plants remote from lignite resources, ashes from biomass-fired grate boilers are a remarkably effective and economical substitute. About 85% of NO reduction efficiency appears achievable at a stoichiometric ratio 0.945. The raw-material cost estimates of the mixed-fuel technology suggest that it could be competitive with selective catalytic reduction (SCR).

The variables, kinetics, and mechanisms of heterogeneous reburning were studied in a flow reactor with a simulated flue gas. The efficiency of heterogeneous reburning depends on the origin of the char, char preparation history and the presence of oxidants, CO2 and O2, and the reducing agent CO, in reburning. Estimated intrinsic rate constants for surface NO reduction in various gaseous environments were compared with those published. In addition to its large surface area, the effectiveness of lignite char appears to be due to its ability to promote two consecutive reactions: (1) the gasification of char by CO2 and O2 for production of CO; (2) the removal of surface oxygen complexes, including those formed after adsorption of NO, by gaseous CO, for the regeneration of reactive sites. Moreover, lignite ash also catalyzes the decomposition of HCN, a major intermediate of NO conversion during gas reburning. These observations suggest that reburning by a mixed fuel containing natural gas and lignite char can be a potentially attractive route for the in–furnance control of nitrogen oxide.

A drug release process by the oral route is random in nature and thus is subject to constant fluctuations. Moreover, individuals have varied tolerances to such fluctuations. The objective of this work is to characterize these fluctuations by a stochastic formalism. The system under consideration, i.e., the gastrointestinal tract consists of four consecutive compartments, i.e., stomach, duodenum, jejunum, and ileum. The master equation of the system as well as the governing equations for the means, variances, and covariances of the random variables, each representing the number of microspheres in an individual compartment, have been derived through the probabilistic population balance. These equations have been numerically solved to predict the total release fraction of drug and its internal fluctuations, and the dynamic statistics (means, variances, and covariances) of the amount of drug in each compartment at any time after administration. The dissolution-intensity functions in the model have been recovered from the available in vitro dissolution data from controlled-release pellets of isosorbide-5-nitrate (IS-5-N) by assuming that the rate of release is of the first order. The residence times and transition-intensity functions of drug in the individual compartments have been estimated from the available data generated by the gamma scintigraphies of IS-5-N pellets labeled by 111 In . Based on these parameters, the total numbers of dissolved drug microspheres and their fluctuations at any instance have been calculated. The model is in accord with the existing in vivo dissolution data of the same drug independently obtained through plasma analysis. More important, the model predicts that fluctuations in terms of the standard deviations of the numbers of particles in the duodenum, jejunum, and ileum can be of the same orders of magnitude as the corresponding mean numbers when 100 microspheres are simultaneously administered orally; in practice, such fluctuations characterized by these deviations could result in an undesirable release profile. Discussion is given of the potential direct clinical application of the results obtained as well as the plausible indirect application of these results and the model derived to the analyses of chemical and biochemical reactors.

Pyrolysis occurs in the initial stage of coal combustion where the volatile tar is generated. An important property of this volatile tar is its molecular-weight distribution. Coal tar contains varying sizes of monomers which are connected by linkages of varying strengths, thereby necessitating a stochastic approach. The present work has adopted the stochastic population balance of the system to derive the master equation for predicting the statistics of this molecular weight distribution of tar as functions of time. The tar produced during pyrolysis is assumed to undergo decomposition to low molecular weight compounds. Moreover, the system containing all tar molecules is lumped into a limited number of states, each representing a particular molecular weight range. The equations for the means, variances, and covariances of the random variables, each representing the number of tar molecules in an individual state in the system, have been derived from the master equation. The model has been compared with the experimental data obtained with both a heated-grid reactor and an entrained-flow reactor to recover the major parameters of the model, i.e. the transition and exit intensity functions. The transition intensity functions exhibit the temperature dependence of the Arrhenius type.

The adsorption of molecules of organic or inorganic compounds in an aqueous solution onto granular activated carbon involves a sequence of steps including: transfer of the molecules from the bulk phase of solution through the relatively stagnant, layer of solution adjacent to the external surface and solution in macropores and micropores of the pellet of activated carbon and occupation of the active sites on the inside of the pellet by the molecules. The present work analyzes and models this sequence of steps by resorting to the stochastic population balance of the numbers of molecules of adsorbate in the three states. The first comprises the bulk phase of the solution; the second, the layer of solution adjacent to the external surface and the solution in the macropores; and the third, the active sites on the inside surfaces of the micropores. The master equation has been derived for the case of a single adsorbate compound. The equations for the means, variances, and covariances of the random variables have been obtained through the system size expansion of the master equation. At equilibrium, the equations for the means reduce to the equation of the Langmuir isotherm. The unknown parameters in the equations for the means have been estimated by comparing the calculated results with the experimental data. These parameters have been adopted to predict the evolution of variances and covariances of the numbers of adsorbate molecules in the three states.

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.

The breakage of coal particles into smaller fragments during the devolatilization stage mostly occurs randomly due to the heterogeneous structure of coal, thereby necessitating a stochastic approach for modeling. In the present work, the master equation approach has been proposed for predicting the statistics of the size distribution of the coal particles during their stepwise degradation. The particle-size distribution has been lumped into a limited number of states, each representing a particular volume range. The master equation and the equations for the means, variances, and covariances of the random variables, each representing the number of particles in the individual states in the system, have also been derived from the stochastic population balance. Simulation has been performed with a stiff differential equation solver to predict the dynamic particle number statistics at any time. By fitting the model to experimental data, the transition intensity function is found to be inversely proportional to the square of particle radius.

The ability to determine combustion and thermal decomposition (pyrolysis) products at trace concentrations can lead to important information on catalytic pathways, the degradation process itself, and structural (fingerprint) information on the parent molecule(s), among others. Gas chromatography coupled with mass spectrometry (GC/MS) is well suited to separate and identify the volatile molecules and molecular fragments generated by combustion and pyrolysis processes. Whereas, pyrolysis (conducted in an inert atmosphere) is often used as a sample introduction device directly coupled to GC/MS, combustion is generally carried out offline and its products are collected and analyzed with GC/MS, or even pyrolysis-GC/MS. In the past few years, this powerful technique has been used to examine a variety of sample types for quite diverse applications. This chapter describes the state of the art and the progress of GC/MS for the measurement of combustion and pyrolysis products. An introduction to the technique, including the principles of GC/MS, is first provided, followed by a demonstration of the instrument's capabilities for combustion and pyrolysis research. All reports discussed herein were selected in part to demonstrate the diversity of current combustion and pyrolysis research using GC/MS. The present authors' studies with temperature-programmed desorption in conjunction with GC/MS to characterize oxygen shuttling on the chars derived from different gaseous environment, are highlighted. Finally, the use of GC/MS in combination with isotope-labeling techniques to reveal complex reaction pathways and mechanisms is discussed. Keywords: Gas chromatography; mass spectrometry; combustion; pyrolysis; temperature-programmed desorption

The effect of reburning fuel type on the partitioning of fixed-nitrogen species in the fuel-rich stage of reburning was studied in a bench scale flow reactor. Methane, hexane, benzene, bituminous coal, and lignite were used as reburning fuels. A simulated flue gas consisting of CO 2 (16.8%), 0 2 (1.95%), NO (1000ppm), and helium was used for experiments at 1100 o C and ca. 0.2s residence time. The total fixed nitrogen (TFN) speciation was found to depend strongly on fuel type ans stoichiometric ratio (SR). Rich stoichiometries promoted conversion of NO to HCN, whereas conversion of HCN to N 2 was promoted by lean stoichiometries. In this stimulated reburning stage, the optimum stoichiometry of TFN production for gaseous fuels was ca. SR=0.95

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).

Recent studies of heterogeneous reburning, i.e., reburning involving a coal-derived char, have elucidated its variables, kinetics and mechanisms that are valuable to the development of a highly efficient reburning process. Young lignite chars contain catalysts that not only reduce NO, but they also reduce HCN that is an important intermediate that recycles to NO in the burnout zone. Gaseous CO scavenges the surface oxides that are formed during NO reduction, regenerating the active sites on the char surface. Based on this mechanistic information, cost-effective mixed fuels containing these multiple features has been designed and tested in a simulated reburning apparatus. Remarkably high reduction of NO and HCN has been observed and it is anticipated that mixed fuel will remove 85% of NO in a three-stage reburning process.

Nitrogen oxides (NO x ) and sulfur oxides (SO x ) emissions are primary contributors to acid rain, which is associated with a number of effects including acidification of lakes and streams, accelerated corrosion of buildings, and visibility impairment. Among the various nitrogen oxides emitted from stationary combustion; nitrogen oxide (NO), nitrous oxide (N2O), and nitrogen dioxide (NO2) are stable, and NO predominates (over 90%). In health effects, NO2 can irritate the lungs and lower resistance to respiratory infection. In the area of ozone nonattainment, NO x and volatile organic compounds (VOCs) react in the atmosphere to form ozone, a photochemical oxidant and a major component of smog. Atmospheric ozone can cause respiratory problems by damaging lung tissue and reducing lung function 1.

In this work, the dispersion of CO and CO 2 from temperature-programmed desorption of char before they reach the mass spectrometer is sequentially examined by a set of methods

Reburning is an emerging three-stage combustion technology designed for the reduction of NO by introducing a small amount of reburning fuel above the primary flame where the majority of NO is chemically reduced to nitrogen. While coal, in general, has not been considered an effective reburning fuel, research at the University of Mississippi suggested that lignite has a reburning efficiency even higher than that of methane. Furthermore, heterogeneous mechanisms are more important than homogeneous mechanisms for char/NO reaction. The objectives of this research are to investigate: (1) implications of pore structure analysis, (2) parameters governing heterogeneous reactions, and (3) estimation of rates of NO reduction and mass transfer limitations. Experiments have been performed in a flow reactor with a simulated fuel gas at a stoichiometric ratio (SR) 1.1. Reburning fuels in this study include chars derived from Pittsburgh No.8 bituminous coal and Mississippi lignite. Chars were produced in N{sub 2} by suspending a sample basket in a tube furnace. Pore structure analyses include BET-N{sub 2}, BET-CO{sub 2}, and DR-CO{sub 2} surface pore size distribution, micropore volume, total pore volume, and average pore radius. These studies suggest that neither BET-N{sub 2} nor DR- CO{sub 2} surface area is a normalization factormore » of chars of different origin. Reaction with NO leads to closures of pores, which may be contributed by formation of surface complexes.« less

The four major tasks conducted during this quarter include: (1) extensive investigation in pore structures of chars before and after reactions with NO , CO,, and 02, (2) effects of pyrolysis time on char reactivities, (3) estimations of rates of NO reduction and mass transfer limitations, and, (4) char reactivities at low feed NO concentrations. Pore structure analyses include BET-N{sub 2}, BET-CO{sub 2}, and DR-CO{sub 2} surface areas, pore size distribution, micropore volume, total pore volume, and average pore radius. These studies suggest that neither BET-N{sub 2} nor DR-CO{sub 2} surface area is a normalization factor of chars of different origin. Parameter study reveals that the effectiveness of heterogeneous reburning strongly depends on variables in three areas: (1) the origin of char, (2) char devolatilization temperature and time, and, (3) the competitions of NO with C0{sub 2} and 02 for the active sites on the char surface. The studies on pore structure and on parameter screening signify the importance of transient kinetics (TK) and temperature programmed desorption (TPD) in the future research. These two techniques all lead to the direct measurements of both stable and reactive surface oxygen complexes, reactive surface area, and the Langmuir-Hinshelwood model which has both importance to both fundamental understanding of reaction mechanisms and to industrial practice. Estimation of rate of NO reduction has been established to include the conversions in the nonisothermal and isothermal regions of the flow reactor, and internal mass transfer limitations. Solving a set of equations simultaneously with MathCad gives frequency factor, activation energy, Thiele modulus, and effectiveness factor.

During this quarter, we have investigated rates and product compositions of NO reduction on chars in gases. N{sub 2} and CO{sub 2} internal surface areas of chars, selected from runs of various pyrolysis and reaction conditions have been measured to assist in interpreting the experimental results. Implications of Langmuir- Hinshelwood mechanisms and mass transfer limitations were examined. Oxidants suppress NO reduction on bituminous coal char more than on lignite char. Observations suggest that NO adsorption and desorption of stable surface oxygen complexes are potentially important rate- limiting steps and may be catalyzed by mineral matter during reburning with lignite char. Relative inert nature of lignite char to CO{sub 2} presence may have potential value in use of fuel system involving both solid and volatile fuels. Lignite char produced at 950 C and zero holding time has higher reactivity than that produced at 1100 C and 5 min holding time. Bituminous coal chars produced at these two conditions, however, have similar reactivity with NO. Internal surface areas of both type chars vary with pyrolysis conditions and gas composition in the subsequent reaction. When oxidants are introduced in the feed, internal surface areas of these two chars vary in opposite directions.

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.