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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 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.

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.

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.

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.

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.

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 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.