Development of a chemical kinetic model for a biosolids fluidized-bed gasifier and the effects of operating parameters on syngas quality

In an effort to decrease the land disposal of sewage sludge biosolids and to recover energy, gasification has become a viable option for the treatment of waste biosolids. The process of gasification involves the drying and devolatilization and partial oxidation of biosolids, followed closely by the reduction of the organic gases and char in a single vessel. The products of gasification include a gaseous fuel composed largely of N₂, H₂O, CO₂, CO, H₂, CH₄, and tars, as well as ash and unburned solid carbon. A mathematical model was developed using published devolatilization, oxidation, and reduction reactions, and calibrated using data from three different experimental studies of laboratory-scale fluidized-bed sewage sludge gasifiers reported in the literature. The model predicts syngas production rate, composition, and temperature as functions of the biosolids composition and feed rate, the air input rate, and gasifier bottom temperature. Several data sets from the three independent literature sources were reserved for model validation, with a focus placed on five species of interest (CO, CO₂, H₂, CH₄, and C₆H₆). The syngas composition predictions from the model compared well with experimental results from the literature. A sensitivity analysis on the most important operating parameters of a gasifier (bed temperature and equivalence ratio) was performed as well, with the results of the analysis offering insight into the operations of a biosolids gasifier.

Implications:

As gasification becomes a more prominent waste disposal option, understanding the effects of feedstock composition and gasifier parameters on the production of syngas (rate and quality) becomes increasingly important. A model has been developed for the gasification of dried sewage sludge that will allow for prediction of changes in syngas quality (and energy recovery from the waste), and should be helpful in assessing the benefits of new gasification projects.     

Modeling and model performance evaluation of sewage sludge gasification in fluidized-bed gasifiers using Aspen Plus

A model was developed to simulate the sewage sludge gasification in an atmospheric fluidised bed gasifier using Aspen Plus. The model here presented was based on the Gibbs free energy minimisation and the restricted equilibrium method was used to calibrate it against previously published experimental data obtained in a lab-scale gasification plant. A sensitivity analysis of the model was carried out by modifying parameters such as the temperature, equivalence ratio (ER) and the steam-to-biomass ratio. The modeled results were in good agreement with the experimental data (especially when air was used as gasifying agent) and reproduced satisfactorily the experimental trends found for the gas composition, the carbon conversion (Xc) and the cold gas efficiency (CGE) under different gasification conditions. Operating at higher temperatures increased the production of H₂ and CO, as well as the Xc and the CGE. The increase in ER produced higher Xc, yet the CGE experienced slight changes due to a decrease in the lower heating value of the resulting syngas, as well as the oxidation of combustible gases. The use of air+steam as gasifying agent increased the H₂ content of the produced gases but decreased the accuracy of the model.

Implications: Gasification is an available alternative to produce energy as well as several raw materials from sewage sludge. The syngas obtained from this technology totally depends on the type of gasifier and the operation conditions, which can be optimized with the help of models. In this work, a relatively simple model was built using ASPEN PLUS. Despite its simplicity, the outputs of the model are in good agreement with experimental results what makes its use interesting for assessing scaling-up possibilities from lab-scale to pilot-scale gasification processes.     

Woody biomass and RPF gasification using reforming catalyst and calcium oxide

This study focused on steam gasification and reforming of waste biomass using a reforming catalyst. The purpose of the study was to evaluate the durability of a commercial Ni reforming catalyst and the effect of CaO on the reforming behavior, and to clarify detailed factors of catalytic performance, as well as the effect of operating parameters on the characteristics of produced gas composition. Moreover, catalyst regeneration was carried out and the behavior of catalytic activity based on gas composition was investigated. Using a fluidized bed gasifier and a fixed bed reformer, gasification and reforming of waste biomass were carried out. Commercial Ni-based catalyst and calcined limestone (CaO) were applied to the reforming reaction. Temperature of the gasifier and reformer was almost 1023 K. Ratio of steam to carbon in the feedstock [mol mol⁻¹] and equivalence ratio (i.e., ratio of actual to theoretical amount of oxygen) [-] were set at about 2 and 0.3, respectively. The feed rate of the feedstock into the bench-scale gasifier was almost 15 kg h⁻¹. The results of waste biomass gasification confirmed the improvement in H₂ composition by the CO₂ absorption reaction using the reforming catalyst and CaO. In addition, CaO proved to be especially effective in decreasing the tar concentration in the case of woody biomass gasification. Catalytic activity was maintained by means of catalyst regeneration processing by hydrogen reduction after air oxidation when woody biomass was used as feedstock.     

Catalytic gasification of biomass (<Emphasis Type="Italic">Miscanthus</Emphasis>) enhanced by CO<Subscript>2</Subscript> sorption

The main objective of this work concerns the coupling of biomass gasification reaction and CO₂ sorption. The study shows the feasibility to promote biomass steam gasification in a dense fluidized bed reactor with CO₂ sorption to enhance tar removal and hydrogen production. It also proves the efficiency of CaO-Ca₁₂Al₁₄O₃₃/olivine bi-functional materials to reduce heavy tar production. Experiments have been carried out in a fluidized bed gasifier using steam as the fluidizing medium to improve hydrogen production. Bed materials consisting of CaO-based oxide for CO₂ sorption (CaO-Ca₁₂Al₁₄O₃₃) deposited on olivine for tar reduction were synthesized, their structural and textural properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and temperature-programmed reduction (TPR) methods, and the determination of their sorption capacity and stability analyzed by thermogravimetric analysis (TGA). It appears that this CaO-Ca₁₂Al₁₄O₃₃/olivine sorbent/catalyst presents a good CO₂ sorption stability (for seven cycles of carbonation/decarbonation). Compared to olivine and Fe/olivine in a fixed bed reactor for steam reforming of toluene chosen as tar model compound, it shows a better hydrogen production rate and a lower CO₂ selectivity due to its sorption on the CaO phase. In the biomass steam gasification, the use of CaO-Ca₁₂Al₁₄O₃₃/olivine as bed material at 700 °C leads to a higher H₂ production than olivine at 800 °C thanks to CO₂ sorption. Similar tar concentration and lighter tar production (analyzed by HPLC/UV) are observed. At 700 °C, sorbent addition allows to halve tar content and to eliminate the heaviest tars.     

Dry reforming of methane to syngas: a potential alternative process for value added chemicals—a techno-economic perspective

During the past decade, there has been increasing global concern over the rise of anthropogenic CO₂ emission into the Earth’s atmosphere (J Air Waste Manage Assoc 53:645–715, 2003). The utilization of CO₂ to produce any valuable product is need of the hour. The production of syngas from CO₂ and CH₄ seems to be one of the promising alternatives in terms of industrial utilization, as it offers several advantages: (a) mitigation of CO₂, (b) transformation of natural gas and CO₂ into valuable syngas, and (c) producing syngas with H₂/CO ratio 1 which may further be used for the production of valuable petrochemicals (J Air Waste Manage Assoc 53:645–715, 2003). A conceptual design for the production of synthesis gas by dry reforming of methane is presented here. An economic assessment of this process with an integrated methanol production section as a case was conceptualized and compared with the conventional steam methane reforming route to produce methanol. The economic study indicated that dry reforming of natural gas/methane is a competitive process with lower operating and capital costs in comparison with steam reforming assuming negligible cost of CO₂ import.     

The study on biomass fraction estimate methodology of municipal solid waste incinerator in Korea

In Korea, the amount of greenhouse gases released due to waste materials was 14,800,000 t CO₂eq in 2012, which increased from 5,000,000 t CO₂eq in 2010. This included the amount released due to incineration, which has gradually increased since 2010. Incineration was found to be the biggest contributor to greenhouse gases, with 7,400,000 t CO₂eq released in 2012. Therefore, with regards to the trading of greenhouse gases emissions initiated in 2015 and the writing of the national inventory report, it is important to increase the reliability of the measurements related to the incineration of waste materials.

This research explored methods for estimating the biomass fraction at Korean MSW incinerator facilities and compared the biomass fractions obtained with the different biomass fraction estimation methods. The biomass fraction was estimated by the method using default values of fossil carbon fraction suggested by IPCC, the method using the solid waste composition, and the method using incinerator flue gas.

The highest biomass fractions in Korean municipal solid waste incinerator facilities were estimated by the IPCC Default method, followed by the MSW analysis method and the Flue gas analysis method. Therefore, the difference in the biomass fraction estimate was the greatest between the IPCC Default and the Flue gas analysis methods. The difference between the MSW analysis and the flue gas analysis methods was smaller than the difference with IPCC Default method. This suggested that the use of the IPCC default method cannot reflect the characteristics of Korean waste incinerator facilities and Korean MSW.

Implications: Incineration is one of most effective methods for disposal of municipal solid waste (MSW). This paper investigates the applicability of using biomass content to estimate the amount of CO₂ released, and compares the biomass contents determined by different methods in order to establish a method for estimating biomass in the MSW incinerator facilities of Korea. After analyzing the biomass contents of the collected solid waste samples and the flue gas samples, the results were compared with the Intergovernmental Panel on Climate Change (IPCC) method, and it seems that to calculate the biomass fraction it is better to use the flue gas analysis method than the IPCC method. It is valuable to design and operate a real new incineration power plant, especially for the estimation of greenhouse gas emissions.     

Adsorption properties of regenerative materials for removal of low concentration of toluene

A specific type of material, activated carbon fiber (ACF), was modified by SiO₂, and the final products ACF-x were obtained as ACF-12.5, ACF-20, ACF-40, and ACF-80 according to different dosages of tetraethoxysilane (TEOS). The modified material on the ACF surface had a significant and smooth cover layer with low content of silica from scanning electron microscope (SEM) image. The modified ACF-x showed the stronger hydrophobicity, thermal stability, and adsorption capacity, which had almost no effect in the presence of water vapor and no destruction in multiple cycles. ACF-20 was proven as the most efficient adsorbent in humid conditions. The dual-function system composed of the regenerative adsorbents and the combustion catalyst would be efficient in consecutive toluene adsorption/oxidation cycles, in which the combustion catalyst was prepared by the displacement reaction of H₂PtCl₆ with foam Ni. Therefore, the adsorption/catalytic oxidation could be a promising technique in the indoor air purification, especially in the case of very low volatile organic compound (VOC; toluene) concentration levels.

Implications: Exploring highly effective adsorptive materials with less expensive costs becomes an urgent issue in the indoor air protection. ACF-20 modified by SiO₂ with Pt/Ni catalysts shows stronger hydrophobicity, thermal stability, and adsorption capacity. This dual-function system composed of the regenerative materials and the combustion catalyst would be a promising technique in the indoor air purification, especially in the case of removal of very low concentration of toluene.     

Bench-scale gasification of cedar wood – Part I: Effect of operational conditions on product gas characteristics

The present study was conducted within the framework of R&D activities on the development of gasification and reforming technologies for energy and chemical recovery from biomass resources. Gasification of the Japanese cedar wood has been investigated under various operating conditions in a bench-scale externally heated updraft gasifier; this was followed by thermal reforming. Parametric tests by varying the residence times, gasification temperatures, equivalence ratios (ERs) and steam-to-carbon (S/C) ratios were performed to determine their effects on the product gas characteristics. Thermodynamic equilibrium calculations were preformed to predict the equilibrium gas composition and compared with the experimental value.We found that the product gas characteristics in terms of the H₂/CO ratio, CO₂/CO ratio, and CH₄ and lighter hydrocarbons concentrations are significantly affected by the operating conditions used. Increasing the residence time decreased the CO₂/CO ratio; however, a nominal effect was noticed on H₂ concentration as a function of the residence time. At sufficient residence time, increasing the temperature led to higher H₂ yields, CO efficiency and higher heating value (HHV) of the product gas. The presence of steam during gasification effectively enhanced the proportion of H₂ in the product gas. However, higher S/C ratio reduced the HHV of the product gas. Increasing the ER from 0 to 0.3 increased the H₂ yields and CO efficiency and decreased the HHV of the product gas.The evolution of CH₄ and lighter hydrocarbons at low gasification temperatures was relatively higher than that at high temperature gasification. The evolution of CH₄ and lighter hydrocarbons at high gasification temperatures hardly varied over the investigated operating conditions.     

Manganese-cerium oxide (MnOx-CeO2) catalysts supported by titanium-bearing blast furnace slag for selective catalytic reduction of nitric oxide with ammonia at low temperature

A series of manganese-cerium oxide (MnO_x-CeO₂) catalysts supported by Ti-bearing blast furnace slag were prepared by wet impregnation and used for low-temperature selective catalytic reduction (SCR) of NO with NH₃. The slag-based catalyst exhibited high nitrogen oxide removal (deNO_x) activity and wide effective temperature range. Under the condition of NO = 500 ppm, NH₃ = 500 ppm, O₂ = 7–8 vol%, and total flow rate = 1600 mL/min, the Mn-Ce/Slag catalyst exhibited a NO conversion higher than 95% in the range of 180–260 °C. The activity of Mn/Slag catalysts was greatly enhanced with the addition of CeO₂. The results indicated that Ti-bearing blast furnace slag had suitable phase composition as good support of SCR catalyst.

Implications: Ti-bearing blast furnace slag is a kind of industrial waste in China. Much slag was underused and piling up, which could cause many environmental issues, such as enormous waste of titanium and groundwater and soil contamination by heavy metals in leachates. The utilization of slag as the support of SCR catalyst will not only make use of solid waste but also cut down the NO_x emitted from power plant.     

Deodorization of pig manure using lignin peroxidase with different electron acceptors

Odor pollution is a big environmental problem caused by large-scale livestock production in China, and developing a practical way to reduce these odors is pressing. In this study, a combination of 0.2–1.0 U/mL lignin peroxidase (LiP) and one of three peroxides (H₂O₂, CaO₂, 2Na₃CO₃·3H₂O₂) was examined for its efficiency in reducing the release of eight chemicals (propionic acid, isobutyric acid, isocaproic acid, isovaleric acid, phenol, p-cresol, indole, and skatole), NH₃, H₂S, and odor intensity from pig manure. The results showed an approximately 90% reduction in p-cresol, 40–60% reduction in odor intensity, 16.5–40% reduction in indolic compounds, and 25–40% reduction in volatile fatty acids. Being the electron acceptors of LiP, 2Na₃CO₃·3H₂O₂ and CaO₂ performed better than H₂O₂ in reducing the concentration of eight chemicals, NH_3, H₂S, and odor intensity from pig manure. The effect of deodorization can last for up to 72 hr.

Implications: In China, one of the major environmental problems caused by confined feeding is odor pollution, which brings a major threat to the sustainability, profitability, and growth of the livestock industry. To couple the LiP with the electron acceptors, a low–cost, simple, and feasible method for odor removal was established in this study. Based on the study results, a practical treatment method was provided for odor pollution and supply the farm operators a more flexible time to dispose treated manure.     

Catalytic CO2 gasification of rubber seed shell-derived hydrochar: reactivity and kinetic studies

In this study, hydrothermal carbonization (HTC) of a biomass was used as a means to improve the physicochemical properties of rubber seed shell (RSS) and enhance its reactivity in the char-CO₂ gasification reaction, known as the Boudouard reaction (C + CO₂ ? 2CO). Hydrochar samples were developed by hydrothermal treatment of RSS, without separating the solid residue from the liquid product, at 433, 473, 513, and 553 K under autogenous pressure. The CO₂ gasification reactivity of the developed hydrochars was then investigated at different heating rates (5, 10, 20, and 30 K/min) by the non-isothermal thermogravimetric method. The hydrochars revealed higher reactivity and improved gasification characteristics compared to the untreated biomass, while the hydrochar which was filtered from the liquid slurry showed lower reactivity compared to the untreated biomass. This was due to the chemical and structural evolutions of the biomass during hydrothermal treatment as indicated by various analyses. The gasification reactivity of the hydrochar was substantially enhanced by introduction of a catalyst (NaNO₃) during HTC. Kinetic analysis of the char-CO₂ gasification reaction was carried out by applying Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink isoconversional methods, and thermodynamic parameters were also determined. The activation energy of the Na-loaded RSS hydrochar in CO₂ gasification (120–154 kJ/mol) was considerably lower than that of the untreated biomass (153–172 kJ/mol). Thermodynamic studies also confirmed the promoting effect of hydrothermal treatment and catalyst impregnation on enhancement of reactivity of the virgin biomass and reduction of gasification temperature.

     

Public health and components of particulate matter: The changing assessment of black carbon

In 2012, the WHO classified diesel emissions as carcinogenic, and its European branch suggested creating a public health standard for airborne black carbon (BC). In 2011, EU researchers found that life expectancy could be extended four to nine times by reducing a unit of BC, vs reducing a unit of PM_2.5. Only recently could such determinations be made. Steady improvements in research methodologies now enable such judgments.

In this Critical Review, we survey epidemiological and toxicological literature regarding carbonaceous combustion emissions, as research methodologies improved over time. Initially, we focus on studies of BC, diesel, and traffic emissions in the Western countries (where daily urban BC emissions are mainly from diesels). We examine effects of other carbonaceous emissions, e.g., residential burning of biomass and coal without controls, mainly in developing countries.

Throughout the 1990s, air pollution epidemiology studies rarely included species not routinely monitored. As additional PM_2.5. chemical species, including carbonaceous species, became more widely available after 1999, they were gradually included in epidemiological studies. Pollutant species concentrations which more accurately reflected subject exposure also improved models.

Natural “interventions” - reductions in emissions concurrent with fuel changes or increased combustion efficiency; introduction of ventilation in highway tunnels; implementation of electronic toll payment systems – demonstrated health benefits of reducing specific carbon emissions. Toxicology studies provided plausible biological mechanisms by which different PM species, e.g., carbonaceous species, may cause harm, aiding interpretation of epidemiological studies.

Our review finds that BC from various sources appears to be causally involved in all-cause, lung cancer, and cardiovascular mortality, morbidity, and perhaps adverse birth and nervous system effects. We recommend that the U.S. EPA rubric for judging possible causality of PM_2.5. mass concentrations, be used to assess which PM_2.5. species are most harmful to public health.

Implications: Black carbon (BC) and correlated co-emissions appear causally related with all-cause, cardiovascular, and lung cancer mortality, and perhaps with adverse birth outcomes and central nervous system effects. Such findings are recent, since widespread monitoring for BC is also recent. Helpful epidemiological advances (using many health relevant PM_2.5 species in models; using better measurements of subject exposure) have also occurred. “Natural intervention” studies also demonstrate harm from partly combusted carbonaceous emissions. Toxicology studies consistently find biological mechanisms explaining how such emissions can cause these adverse outcomes. A consistent mechanism for judging causality for different PM_2.5 species is suggested.

A list of acronyms will be found at the end of the article.     

How oxygen deficiency in the Baltic Sea proper has spread and worsened: The role of ammonium and hydrogen sulphide

Even large inflows of oxygen-rich seawater to the Baltic Proper have in recent decades given only short-lived relief from oxygen deficiency below the halocline. We analyse long-term changes in oxygen deficiency, and calculate the “total oxygen debt” ΣOD, the oxygen required to oxidize the hydrogen sulphide (H₂S) and ammonium (NH₄) that builds up during stagnation periods. Since the early 1990s, oxygen below 65m has gradually decreased during successive stagnation periods, and the ΣOD has increased, with NH₄ more important than previously recognised. After the major inflow in 2014, the Baltic Proper ΣOD has reached its highest level so far. The gradual shift of the ΣOD to shallower sub-halocline waters in the western and northern basins has increased the risk of periodic coastal hypoxia and export of hypoxic water to the Bothnian Sea. The potential for inflows large enough to more than eliminate the ΣOD seems limited in the near term.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01738-8.     

Experimental research of oily sawdust air gasification

This article shows oily sawdust gasification research on countercurrent installation. Experimental research was on a laboratory scale. The main purpose of the experiment was combustible gas production with higher CH₄ concentration. Gas concentrations like CO, CO₂, CH₄, H₂, and C_nH_m determine syngas composition. The technological parameter’s value defines experimental conditions. Value of this was fuel to air ratio. With fuel to air ratio change, syngas composition was a differential phenomenon where it depended on the process parameters like temperature. Additionally, evaluation of methane formation from CO, H₂, and CO₂ was done. Methanization coefficients were based on CO and CO₂ hydrogenation reactions. Component’s activity was in analogs way to syngas components changed.

     

Characterization of temporal variations in landfill gas components inside an open solid waste dump site in Sri Lanka

A long-term monitoring of composition of landfill gases in the region with high rainfall was conducted using an argon assay in order to discuss air intrusion into the dump site. Gas samples were taken from vertical gas monitoring pipes installed along transects at two sections (called new and old) of an abandoned waste dump site in Sri Lanka. N₂O concentrations varied especially widely, by more than three orders of magnitude (0.046–140 ppmv). The nitrogen/argon ratio of landfill gas was normally higher than that of fresh air, implying that denitrification occurred in the dump site. Argon assays indicate that both N₂ and N₂O production occurred inside waste and more significantly in the old section. The Ar assay would help for evaluations of N₂O emission in developing countries.

Implications: A long-term monitoring of composition of landfill gases in the region with high rainfall was conducted using an argon assay in order to discuss air intrusion into the dump site. Argon assays indicate that both N₂ and N₂O production occurred inside waste and more significantly in the old section.     

Adsorption kinetics and modeling of H2S by treated waste oil fly ash

Waste oil fly ash (OFA) collected from disposal of power generation plants was treated by physicochemical activation technique to improve the surface properties of OFA. This synthesized material was further used for potential hydrogen sulfide (H₂S) adsorption from synthetic natural gas. The raw OFA was basically modified with a mixture of acids (20% nitric acid [HNO₃] and 80% phosphoric acid [H₃PO₄]), and it was further treated with 2 M potassium hydroxide (KOH) to enhance the surface affinity as well as surface area of synthesized activated carbon. Correspondingly, it enhanced the adsorption of H₂S. Crystallinity, surface morphology, and pore volume distribution of prepared activated carbon were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. Fourier transform infrared (FTIR) study was also performed to identify the functional groups during different synthesis stages of modified activated carbon. The Langmuir, Freundlich, Sips, and dual-site Langmuir (DSL) models were used to study the kinetic and breakthrough behavior of H₂S adsorption over alkali-modified activated carbon. Modeling results of isotherms indicated that OFA has dual sites with high and low affinity for H₂S adsorption. The Clark model, Thomas model, and Yoon-Nelson model were used to examine the effects of flow rate and inlet concentration on the adsorption of H₂S. Maximum uptake capacity of 8.5 mg/g was achieved at 100 ppm inlet concentration and flow rate of 0.2 L/min.

Implications: Utilization of worthless oil fly ash from power plant is important not only for cleaning the environment but also for solid waste minimization. This research scope is to eradicate one pollutant by using another pollutant (waste ash) as a raw material. Chemical functionalization of synthesized activated carbon from oil fly ash would lead to attachment of functional groups of basic nature to attract the acidic H₂S. Such type of treatment can enhance the uptake capacity of sorbent several times.     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

Comparison on surface properties and desulfurization of MnO2 and pyrolusite blended activated carbon by steam activation

In this study, MnO₂ and pyrolusite were used as the catalysts to prepare modified activated carbon, that is, AC-Mn and AC-P, respectively, from coals by blending method and steam activation. The Brunauer–Emmett–Teller (BET) results indicated that the AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The relative contents of basic functional groups (i.e., C = O, π-π*) on AC-P were slightly lower than those on AC-Mn, while both contained the same main metal species, namely, MnO. The desulfurization results showed that with 3 wt% of blending ratio, AC-Mn3 and AC-P3 had higher sulfur capacities at 220 and 205 mg/g, respectively, which were much higher than for the blank one (149.6 mg/g). Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn, which might be attributed to the existence of other metals in pyrolusite. After the desulfurization process, MnO were gradually transferred into MnSO₄, and the relative contents of basic functional groups decreased evidently for both AC-Mn3 and AC-P3. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurization.

Implications: MnO₂ and pyrolusite were used as the additives to prepare modified activated carbon from coals by a blending method and by steam activation, that is, AC-Mn and AC-P, respectively. The AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The AC-Mn and AC-P had higher sulfur capacities than a blank one. Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurizatio.     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.