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.     

Concentrations of carbon gases and oxygen and their emission ratios from the combustion of rice hulls in a wind tunnel

Rice hulls are widely burnt in agricultural fields in Asia because it is difficult to find other uses for them. Farmers burn rice hulls usually under incomplete combustion conditions to avoid accidental fires. In this study we investigated carbon gas emissions from rice hull fires at controlled wind speeds in a wind tunnel to clarify the effect of wind on such fires. Burning of the rice hulls resulted in relatively incomplete combustion: the ratio of [CO] to [CO₂] was high, >0.2, except when burning occurred at high wind speeds. Distinct differences in the carbon ratios of emitted carbon gases (CO₂, CO, CH₄, and nonmethane volatile organic compounds [NMVOC]) were found between high and low wind speeds: at high wind speeds, flames were usually present, and the CO₂ contribution to total carbon gases was higher; at low wind speeds, the NMVOC and CH₄ contributions to total carbon gases were greater. Therefore, a compensatory relationship existed between NMVOC and CH₄ and CO₂. Additionally, the ratio of [consumed O₂] to [CO₂] was <1 during the smoldering phase of combustion and >1 during the charcoal phase, synchronous with changes in [CH₄] and [NMVOC].     

Gas reforming and tar decomposition performance of nickel oxide (NiO)/SBA-15 catalyst in gasification of woody biomass

In the gasification of biomass, it is necessary to limit the amount of by-product tar and increase the yields of hydrogen (H₂) and carbon monoxide (CO) (syngas). Therefore, we conducted gasification and reforming experiments on woody biomass using an electric tubular furnace, to evaluate the gas reforming and tar decomposition performance of a NiO/SBA-15 catalyst. As a result, we found that this catalyst is effective for H₂ production. It is believed that the increase in H₂ volume due to the catalyst occurs through a steam reforming reaction involving hydrocarbons, including methane (CH₄), and the water-gas shift reaction. With respect to the influence of the gasifying agent on the reforming effect of the catalyst, the amount of generated carbon dioxide (CO₂) and hydrogen (H₂) increases because the shift reaction is promoted by supplying steam. On the other hand, it was inferred that the shift reaction rarely occurred because it approaches equilibrium by supplying O₂. Furthermore, it is suggested that light aromatic hydrocarbons are decomposed by the catalyst.

Implications: The mesoporous silica catalyst NiO/SBA-15 was highly effective for H₂ production and decomposition of light aromatic compounds in the gasification of woody biomass. In the catalyst reaction, supplying steam promoted H₂ production. From thermodynamic analysis and discussion, it was also inferred that supplying O₂ might prevent the water gas shift reaction. The results are useful for designing a process needed for rich H₂ production and gas refining process for further use of syngas.     

Catalytic Destruction of Dichloromethane Using Perovskite-Type Oxide Catalysts

Abstract

Dichloromethane (DCM, also known as methylene chloride [CH₂Cl₂]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH₂Cl₂ by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH₂Cl₂ (C_o = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O₂ = 5-21%) influence the operational stability and capacity for the removal of CH₂Cl_2.

The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH₂Cl₂ reduction was achieved by the catalytic oxidation over La-CoO₃-based perovskite catalyst at 600 °C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH₂Cl₂ in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

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.     

固体超强酸和金属氧化物类催化剂上CH4-SCR还原NOx研究进展

由于还原剂甲烷价廉易得,甲烷选择性催化还原NO_x（简称CH₄-SCR）被认为是最有潜力替代NH₃-SCR的催化还原技术。现有的CH₄-SCR催化剂中,分子筛类催化剂因催化活性高而被广泛研究,但由于其水热稳定性不好,使得非分子筛负载的催化剂成为近年来的研究热点,其中主要包括固体超强酸和氧化物两大类。综述了这两类催化体系在催化活性、反应机理及掺杂改性等方面的研究现状,比较了各种催化剂的优缺点,并对CH₄-SCR的发展前景进行了展望。     

Incinerating Volatile Organic Compounds with Ferrospinel Catalyst MnFe2O4: An Example with Isopropyl Alcohol

Abstract

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe₂O₄. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe₃O₄]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr^?1, an oxygen (O₂) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 °C.     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

An urban boreal lake basin as a source of CO₂ and CH₄

Up to now, carbon gas fluxes from urban lakes in the boreal zone have seldom been studied. In summer 2005 we investigated fluxes from an urban boreal lake basin in southern Finland with long history of eutrophication and anoxia. Hypolimnetic CO₂ and CH₄ concentrations were high compared to other boreal lakes. During the open-water period, the lake basin acted as a source of CO₂ and CH₄ with fluxes of 2.10 mol m⁻² and 0.04 mol m⁻², respectively. Despite the high oxidation rate (83%), CH₄ flux was higher than in other lakes and CH₄ contributed 60% to Global Warming Potential. The ratio of carbon emission to accumulation was 4, i.e. emissions were an important route for carbon departure but less so than in rural lakes. Since the lake oxygen conditions affected nutrient availability, there was a positive feedback from hypolimnion to carbon uptake, which was reflected in gas concentrations.     

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.     

Catalytic Reduction of Nitrogen Oxides in Automobile Exhaust

The catalytic reduction of oxides of nitrogen from leaded automobile exhaust has been demonstrated to be technically feasible. These studies made with copper-containing catalysts are based upon the reducing nature of exhaust caused by the carbon monoxide present. The reaction involves 2 CO + 2 NO → + N₂ + CO₂ + 178.5 Kcal.     

Carbon dioxide and methane emissions from the scale model of open dairy lots

To investigate the impacts of major factors on carbon loss via gaseous emissions, carbon dioxide (CO₂) and methane (CH₄) emissions from the ground of open dairy lots were tested by a scale model experiment at various air temperatures (15, 25, and 35 °C), surface velocities (0.4, 0.7, 1.0, and 1.2 m sec^?1), and floor types (unpaved soil floor and brick-paved floor) in controlled laboratory conditions using the wind tunnel method. Generally, CO₂ and CH₄ emissions were significantly enhanced with the increase of air temperature and velocity (P < 0.05). Floor type had different effects on the CO₂ and CH₄ emissions, which were also affected by air temperature and soil characteristics of the floor. Although different patterns were observed on CH₄ emission from the soil and brick floors at different air temperature-velocity combinations, statistical analysis showed no significant difference in CH₄ emissions from different floors (P > 0.05). For CO₂, similar emissions were found from the soil and brick floors at 15 and 25 °C, whereas higher rates were detected from the brick floor at 35 °C (P < 0.05). Results showed that CH₄ emission from the scale model was exponentially related to CO₂ flux, which might be helpful in CH₄ emission estimation from manure management.

Implications: Gaseous emissions from the open lots are largely dependent on outdoor climate, floor systems, and management practices, which are quite different from those indoors. This study assessed the effects of floor types and air velocities on CO₂ and CH₄ emissions from the open dairy lots at various temperatures by a wind tunnel. It provided some valuable information for decision-making and further studies on gaseous emissions from open lots.     

生活污水不同进水C/N比负荷对垂直潜流式人工湿地排放温室气体的影响

人工湿地处理的生活污水含氮量或者有机物含量很高时,可能会造成人工湿地在处理污水的过程中排放大量温室气体。研究了垂直潜流式人工湿地在人工合成的生活污水不同污染物进水C/N负荷条件下污水处理效果和温室气体(CO2和CH4)的排放量,利用现场测量和碳平衡模型估算分析了可以达到最佳污水净化效果和最少温室气体排放量的污染物进水C/N负荷条件。结果显示,在进水C/N负荷为C/N=6∶1~9∶1时可以得到最佳的污染物去除率。温室气体CH4排放量较CO2排放量可以忽略不计,而在进水C/N负荷为C/N=3∶1~6∶1时可以实现最少的温室气体排放。综上所述,最优的进水C/N负荷确定为C/N=6∶1,此时人工湿地可以得到较高的污染物去除率而排放较少的温室气体。     

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.     

Macromolecule simulation studies on mechanical properties and CH4/CO2 adsorption characteristics in bituminous coal matrix based on uniaxial tension–compression effect

With the increasing complication of production and geology conditions, and the increase of mining intensity and depth in coal mine, the coal structure presents varying degrees of deformation. In order to study the influence of uniaxial tension–compression effect on mechanical properties of coal matrix and CH₄/CO₂ adsorption characteristics, a macromolecular model reflecting the realistic bituminous coal structure was established. Results demonstrate that the influence of tension strain on the microporous structural parameters is greater than that of compression strain, and the tension strain weakens the mechanical properties but enhances the adsorbates adsorption amount. For the pure gases adsorption, there is a negative linear correlation between the total energy and adsorption amount. Additionally, the strain ranging from??0.20 to 0.20, the distribution of punctated adsorbates density develops to that of banded adsorbates density, and the mean adsorption density and saturated adsorption amount increase linearly. For the binary components adsorption (1:1), the CH₄ adsorption strength increases while the CO₂ adsorption strength slightly decreases. The minimum of total energy decreases in a quadratic polynomial relationship with the strain, and the proportion of van der Waals energy is 75.8–85.5%. Nevertheless, the competitive adsorption and strain have little effect on the potential energy range of the adsorbates. Furthermore, the diffusibility of CO₂ molecular layers is relatively good, and the strain enhances the stability of CH₄ molecular layers for the saturated binary adsorption. The findings provide essential guidance for the improvement of carbon capture and storage and CO₂-enhanced coalbed methane technologies in the deformation area of coal seam.

     

Technique for Measuring the Total Concentration of Gaseous Fixed Nitrogen Species

This paper reports the development of a rapid, continuous technique for analyzing fixed nitrogen species (NH₃, HCN, CH₃NH₂, etc.). The technique uses a platinum catalyst at low pressure in combination with a conventional chemiluminescent NO _x analyzer. Previous workers observed that conventional stainless steel catalysts, and platinum catalysts operated at atmospheric pressure, do not reliably convert NH₃ to NO. The most serious problem was the variation in the efficiency of these catalysts with operating conditions. Changes in temperature, gas composition, or X_NH3 could change the conversion efficiency from 99.9% to <30%. The new conversion technique, however, is quantitative up to several thousand ppm NH₃ in either O₂/He or O₂/CO₂/N₂.     

Hydrogen production using thermocatalytic decomposition of methane on Ni<Subscript>30</Subscript>/activated carbon and Ni<Subscript>30</Subscript>/carbon black

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for CO_x free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni₃₀/AC and Ni₃₀/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).     

Carbon emission from global hydroelectric reservoirs revisited

Substantial greenhouse gas (GHG) emissions from hydropower reservoirs have been of great concerns recently, yet the significant carbon emitters of drawdown area and reservoir downstream (including spillways and turbines as well as river reaches below dams) have not been included in global carbon budget. Here, we revisit GHG emission from hydropower reservoirs by considering reservoir surface area, drawdown zone and reservoir downstream. Our estimates demonstrate around 301.3 Tg carbon dioxide (CO₂)/year and 18.7 Tg methane (CH₄)/year from global hydroelectric reservoirs, which are much higher than recent observations. The sum of drawdown and downstream emission, which is generally overlooked, represents 42 % CO₂ and 67 % CH₄ of the total emissions from hydropower reservoirs. Accordingly, the global average emissions from hydropower are estimated to be 92 g CO₂/kWh and 5.7 g CH₄/kWh. Nonetheless, global hydroelectricity could currently reduce approximate 2,351 Tg CO₂eq/year with respect to fuel fossil plant alternative. The new findings show a substantial revision of carbon emission from the global hydropower reservoirs.     

The change of gaseous carbon fluxes following the switch of dominant producers from macrophytes to algae in a shallow subtropical lake of China

Successions of lake ecosystems from clear-water, macrophyte-rich conditions into turbid states with abundant phytoplankton have taken place in many shallow lakes in China. However, little is know about the change of carbon fluxes in lakes during such processes. We conducted a case study in Lake Biandantang to investigate the change of carbon fluxes during such a regime shift. Dissolved aquatic carbon and gaseous carbon (methane (CH₄) and carbon dioxide (CO₂)) across air–water interface in three sites with different vegetation covers and compositions were studied and compared. CH₄ emissions from three sites were 0.62±0.36, 0.70±0.36, and 1.31±0.57 mg m⁻² h⁻¹, respectively. Correlation analysis showed that macrophytes, rather than phytoplankton, directly positively affected CH₄ emission. CO₂ fluxes of three sites in Lake Biandantang were significantly different, and the average values were 77.8±20.4, 52.2±14.1 and 3.6±26.8 mg m⁻² h⁻¹, respectively. There were an evident trend that the larger macrophyte biomass, the lower CO₂ emissions. Correlation analysis showed that in different sites, dominant plant controlled CO₂ flux across air–water interface. In a year cycle, the percents of gaseous carbon release from lake accounting for net primary production were significantly different (from 39.3% to 2.8%), indicating that with the decline of macrophytes and regime shift, the lake will be a larger carbon source to the atmosphere.     

Catalytic oxidation for air pollution control

Bench-scale experiments have been conducted to evaluate a series of titania-supported Pt-Pd (as oxides) catalysts in the presence and absence of MoO₃ and Fe₂O₃ additives for their effectiveness in the complete catalytic oxidation of volatile organic compounds (VOCs) in air likely to be found in waste gases. Under oxidizing conditions, all of the catalysts promoted the complete oxidation of VOCs to CO₂ and H₂O. 99 % Conversion was achieved with a C₂H₄-C₂H₆ gas mixture in air at temperatures between about 160–450 °C and at a space velocity of 20,000 h^?1. Oxidation activity for the titania supported catalysts were found to decrease in the order Pt-Pd-Mo-Fe > Pt-Pd-Mo > Pt-Pd-Fe > Pt-Pd. However, the addition of MoO₃ and Fe₂O₃ increase the catalyst activity and reduce the reaction temperature for the complete destruction. Ageing was also performed in order to study the stability of the most active catalyst. Pt-Pd-Mo-Fe (as oxides) on titania catalyst is effective in oxidizing a wide range of volatile organic compounds at relatively low temperatures (220–405 °C) and and at a space velocity of 40,000 h^?1 and is resistant to poisoning by halogenated and amine volatile organic compounds.