SynGas production from organic waste using non-thermal-pulsed discharge

The purpose of this study was to develop a technology that can convert biogas to synthesis gas (SynGas), a low-emission substituted energy, using a non-thermal-pulsed plasma method. To investigate the characteristics of SynGas production from simulated biogas, the reforming characteristics in relation to variations in pulse frequency, biogas component ratio (C3H8/CO2), vapor flow ratio (H2O/total flow rate [TFR]), biogas velocity, and pulse power were studied. A maximum conversion rate of 49.1% was achieved for the biogas when the above parameters were 500 Hz, 1.5, 0.52, 0.32 m/sec, and 657 W, respectively. Under the above conditions, the dry basis mole fractions of the SynGas were as follows: H2 = 0.645, CH4 = 0.081, C2H2 = 0.067, C3H6 = 0.049, CO = 0.008 and C2H4 = 0.004. The ratio of hydrogen to the other intermediates in the SynGas (H2/ITMs) was 3.1.     

Effects of CH4 and CO on the reduction of nitric oxide to nitrogen in a discharge reactor

Additives are often added to enhance the efficiency of NO removal. This study uses a radio frequency (rf) discharge to consider the effect of added CH4 and CO to simulated NO/N2/O2/H2O mixtures on the elevation of NO conversion and the reduction of NO into N2. The enhancement levels of NO conversion when using various additives were found to be in this order: +CH4 > +CO > no additive. NO conversion reached 99.3%, 86.2%, and 77.6% when adding CH4, CO, and without additive, respectively, at inlet additive/NO molar ratio (R) = 5 and at 120 W. Moreover, the fraction of total N atoms converted from NO into N2 (FN2) was very high, reaching 99.4% and 99.5% when adding CH4 and CO, respectively, at R = 1 and at 120 W. The better operating conditions are using CH4 as the additive at R > or = 1 and a power of > 60 W to reach a higher NO conversion with a higher FN2. However, it should be noted that this rf plasma approach is not practical at this stage because of its relative low pressure.     

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.     

水蒸气改善钙基CO2吸收剂循环活性的研究

对钙基CO2吸收剂的循环活性改善进行了研究,分析了水蒸气处理对吸收剂的最大转化率、比表面积及孔分布等微观结构变化的影响。结果表明,经水蒸气处理后,钙基CO2吸收剂的循环活性得到了改善,最大转化率比未经水蒸气处理可提高约50百分点;水蒸气处理可大大提高钙基CO2吸收剂的比表面积,并有效改善其孔径分布状态,可使其稳定保持较高的转化率;含碳能源直接制氢过程可在不需要任何添加剂或辅助手段的条件下,有效保持钙基CO2吸收剂的循环活性。     

水碳比变化对汽油氧化重整制氢影响的研究

本文用正辛烷代替汽油从理论和实验两方面研究了水碳比变化对汽油氧化重整制氢反应的影响。理论研究表明 ,在绝热反应条件下 ,对应确定的反应温度存在一个最佳的氧油比及水碳比 ;实验研究表明 ,在非绝热反应体系中 ,在一定的氧油比及反应温度条件下 ,反应体系的转化率及生成氢的选择性均随水碳比的增加而增加 ,为实现燃料电池汽油制氢自热反应 ,反应体系应在一定水碳比条件下进行 ,实验条件下最佳的水碳比范围是 1.5— 2 .5之间。     

Performance of a semi-industrial scale gasification process for the destruction of polychlorinated biphenyls

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spectrometry. The coplanar PCBs congeners 77, 105, 118, 156/ 157, and 167 were detected in the syngas at concentrations < 2 x 10(-7) mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was > 99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 x 10(-6) ng-toxic equivalent (TEQ)/m3 and 7.1 x 10(-6) ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).     

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.     

Pathway of CH4 formation in anoxic rice field soil and rice roots determined by 13C-stable isotope fractionation

In anoxic rice fields methane is produced by either reduction of CO2 or cleavage of acetate. We measured the delta 13C-values of CH4 and CO2, acetate and organic carbon during time course experiments with anoxic methanogenic soil and root samples and used these values to calculate the fractions of CH4 (and acetate) produced from CO2 reduction. Comparison with radiotracer and/or inhibitor studies constrained the kinetic fractionation factors used for calculation. The fractionation factors for the conversion of CO2 to CH4 and of acetate to CH4 were on the order of alpha = 1.07 (epsilon = -70%) and epsilon > or = - 20%, respectively. The pathway of CH4 production changed with time of anoxic incubation. Anoxic slurries of rice field soil first produced CH4 predominantly (>50%) from CO2, then predominantly (>80%) from acetate and finally (after about one month) according to the theoretically expected ratio (33% CO2 and 67% acetate). Anoxic rice roots, on the other hand, initially produced CH4 exclusively from CO2, followed by contribution of acetate of about 40-60%. Rice roots also produced acetate that partially originated (< or = 1 30%) from reduction of CO2 as determined by calculation of isotopic fractionation using fractionation factors from the literature. The results demonstrate that there is quite some variability in pathways of CH4 production, and also indicate that isotopic fractionation factors may be different in different habitats and change with time.     

Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Performance of an innovative two-stage process converting food waste to hydrogen and methane

This study was conducted to evaluate the performance of an innovative two-stage process, BIOCELL, that was developed to produce hydrogen (H2) and methane (CH4) from food waste on the basis of phase separation, reactor rotation mode, and sequential batch technique. The BIOCELL process consisted of four leaching-bed reactors for H2 recovery and post-treatment and a UASB reactor for CH4 recovery. The leaching-bed reactors were operated in a rotation mode with a 2-day interval between degradation stages. The sequential batch technique was useful to optimize environmental conditions during H2 fermentation. The BIOCELL process demonstrated that, at the high volatile solids (VS) loading rate of 11.9 kg/m3 x day, it could remove 72.5% of VS and convert VS(removed) to H2 (28.2%) and CH4 (69.9%) on a chemical oxygen demand (COD) basis in 8 days. H2 gas production rate was 3.63 m3/m3 x day, while CH4 gas production rate was 1.75 m3/m3 x day. The yield values of H2 and CH4 were 0.31 and 0.21 m3/kg VS(added), respectively. Moreover, the output from the post-treatment could be used as a soil amendment. The BIOCELL process proved to be stable, reliable, and effective in resource recovery as well as waste stabilization.     

VOC destruction by water diluted hydrogen mild combustion

This study represents a preliminary numerical evaluation of the effect of steam dilution and hydrogen addition on the oxidation of formaldehyde and benzene, chosen as representative of the volatile organic compounds (VOC), in mild condition by evaluating the autoignition time and the steady state attainment. These parameters are important in the design of thermal VOC destruction plants since they influence the abatement efficiency and, therefore, the plant dimension. It has come out that, in comparison with the system diluted in nitrogen, steam induces lower autoignition times and, on the other hand, longer times for the attainment of the steady state. In contrast, for very high water content the autoignition time slightly increases. In particular results have shown that is possible to identify an optimum value of steam content that allows for the attainment of the steady state condition by the lowest residence time. Hydrogen addition to systems diluted in nitrogen promotes the oxidation reactions and anticipates the steady state condition. In steam diluted systems hydrogen delays the autoignition of the mixtures even though anticipates the attainment of the complete destruction of the VOC. The rate of production analysis has showed that the H(2)/O(2) reactions, that promote the ignition and the destruction of VOC, are sensibly modified by the presence of water and hydrogen.     

低温等离子体催化氧化甲烷的实验研究

采用电容耦合等离子体和催化剂协同作用对干空气中的甲烷进行了氧化实验，并和没有放置催化剂时进行了对比，结果表明，放置催化剂后甲烷的分解效率明显提高，反应产物中CO2的选择性增加，副产物NO和NO2的浓度减少．反应所需的能耗降低。甲烷的最终氧化产物为CO、CO2和H2O。     

Anaerobic bioconversion of carbon dioxide to biogas in an upflow anaerobic sludge blanket reactor

The increasing concentration of carbon dioxide (CO2)--the most dominant component of greenhouse gases--in the atmosphere has been of growing concern for many years. Many methods focus on CO2 capture and storage and there is always the risk of CO2 release to the environment. In this study, a new method to convert CO2 to biogas with a high content of methane (CH4) in an anaerobic system with a lab-scale upflow anaerobic sludge blanket reactor at 35 degrees C was developed. In a series of experiments, the reactor was run with and without CO2-saturated solutions including volatile fatty acids (VFAs) as sources of hydrogen. The concentration of dissolved CO2 in the influent solutions was 2.2-6.1 g/L, with corresponding chemical oxygen demand (COD) values of 2.6-8.4 g/L for the solutions. Overall CO2 removal values of 2.7-20 g/day (49-88% conversion) were obtained for the organic loading rates (OLR) and CO2 loading rates of 8-36 gCOD/L day and 6-26 gCO2/L x day, respectively with CH4 purity of above 70%. Also, VFA and COD removal were in the range of 79-95% and 75-90%, respectively. Methanogenic activities of the cultures with the concentrations measured as volatile suspended solids (VSSs) were 0.12-0.40 L CH4/gVSS x d with the highest value for the system containing acetic acid. This anaerobic method can be applied to reduce CO2 emitted to the atmosphere from a wide variety of industrial point sources with a value-added product, CH4.     

Bio-syngas production with low concentrations of CO2 and CH4 from microwave-induced pyrolysis of wet and dried sewage sludge

This paper assesses the feasibility of producing syngas from sewage sludge via two pyrolysis processes: microwave-induced pyrolysis (MWP) and conventional pyrolysis (CP). The changes in the composition of the produced gas as a function of the pyrolysis treatment and the initial moisture content of the sludge were evaluated. It was found that MWP produced a gas with a higher concentration of syngas than CP, reaching values of up to 94vol%. Moreover, this gas showed a CO2 and CH4 concentration around 50% and 70%, respectively, lower than that obtained in the gas from CP. With respect to the effect of moisture on gas composition, this was more pronounced in CP than in MWP. Thus, the presence of moisture increases the concentration of H2 and CO2 and decreases that of CO, especially when CP was used. In order to elucidate the behaviour of CO2 during the pyrolysis, the CO2 gasification kinetics of the char obtained from the pyrolysis were investigated. It was established that in microwave heating the gasification reaction is much more favoured than in conventional heating. Therefore, the low concentration of CO2 and the high concentration of CO in the microwave pyrolysis gas could be due to the self-gasification of the residue by the CO2 produced during the devolatilization of the sewage sludge in the pyrolysis process.     

Catalytic gasification of coal using eutectic salts: recovery,regeneration, and recycle of spent eutectic catalysts

Catalyst recovery studies were conducted for gasified chars produced from steam gasification of Illinois #6 coal catalyzed with two different catalyst systems. A ternary (43.5 mol% Li2CO3-31.5 mol% Na2COr-25 mol% K2CO3) and a binary (29 mol% Na2CO3-71 mol% K2CO3) eutectic catalyst system were used for gasifying coal. Various extraction schemes, such as water extraction, H2SO4 extraction, and acetic acid extraction, were evaluated with respect to their extraction efficiencies. Effects of major process variables, such as solvent-to-char ratio, mixing time, temperature, and concentration, on the extraction efficiency were evaluated. A process schematic for the entire catalyst recovery, regeneration, and recycle scheme was developed and the preliminary process economics were determined based on these extraction schemes. H2SO4 extraction was found to be the most desirable. It also turned out to be more attractive than a once-through throwaway system.     

Catalytic performance of Ag/Al2O3-C2H5OH-Cu/Al2O3 system for the removal of NOx from diesel engine exhaust

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4% Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst 10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and 10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH addition, the diesel engine completely meets EURO III emission standards.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

底物初始浓度对光合细菌产氢动力学特性的影响

实验研究了底物初始浓度对光合细菌产氢动力学特性的影响，并对光合细菌产氢得率和初始底物转化为氢气得率进行比较，分析底物初始浓度对光合细菌产氢代谢的影响，实验发现底物初始浓度为120 mmol/L时最适合光合细菌的产氢代谢，底物初始浓度达到140 mmol/L时，光合细菌主要进行生物量合成和产酸代谢，得到各浓度梯度下的最大生物量，但对产氢代谢产生抑制作用，表明最大生物量与最大的产氢能力之间不成正比关系及光合细菌产生CO2机制与产氢机制不同；光合细菌最大比产氢活性表现在对数生长期，最大生物量出现在稳定期。实验证明，光合细菌对数生长期受底物浓度影响大，底物浓度低，最大生物量所对应的时间相对较早，底物浓度增大，最大生物量所对应的时间相对延后。     

用H2O2/Fe^3＋处理高浓度含甲醛废水的研究

研究采用H2O2/Fe^3＋催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H2O2/COD（质量比）=2.2～2.6,Fe^3＋/H2O2（摩尔比）=0.048～0.058,反应pH1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H2O2/Fe^3＋处理含甲醛废水具有比采用H2O2/Fe^2＋较优的效果。     

Harnessing dark fermentative hydrogen from pretreated mixture of food waste and sewage sludge under sequencing batch mode

Food waste and sewage sludge are the most abundant and problematic organic wastes in any society. Mixture of these two wastes may provide appropriate substrate condition for dark fermentative biohydrogen production based on synergistic mutual benefits. This work evaluates continuous hydrogen production from the cosubstrate of food waste and sewage sludge to verify mechanisms of performance improvement in anaerobic sequencing batch reactors. Volatile solid concentration and mixing ratio of food waste and sludge were adjusted to 5 % and 80:20, respectively. Five different hydraulic retention times (HRT) of 36, 42, 48, 72, and 108 h were tested using anaerobic sequencing batch reactors to find out optimal operating condition. Results show that the best performance was achieved at HRT 72 h, where the hydrogen yield, the hydrogen production rate, and hydrogen content were 62.0 mL H₂/g VS, 1.0 L H₂/L/day, and ~50 %, respectively. Sufficient solid retention time (143 h) and proper loading rate (8.2 g COD/L/day as carbohydrate) at HRT 72h led to the enhanced performance with better hydrogen production showing appropriate n-butyrate/acetate (B/A) ratio of 2.6. Analytical result of terminal-restriction fragment length polymorphism revealed that specific peaks associated with Clostridium sp. and Bacillus sp. were strongly related to enhanced hydrogen production from the cosubstrate of food waste and sewage sludge.