采用固体氧化物燃料电池反应器脱除H2S

采用固体氧化物燃料电池反应器脱除H2S,反应器以Co-Mo双元硫化物作电催化剂,Zr掺杂的BaCeO3（BCZY）为固体电解质。研究了燃料电池的燃料气流量、反应温度和电流密度等参数对H2S去除率的影响。结果表明：在反应温度为800℃、燃料气流量为30mL／min的条件下,H2S去除率达71％;在测量的电流密度区间内,H2S去除率与电流密度之间呈线性关系。电能回收实验结果表明,当采用掺杂5％（质量分数）BCZY的Co—Mo双元硫化物作为阳极时,单体燃料电池输出电压达0．68V,最大电功率密度为3．5mW／cm2。因此,燃料电池技术脱除H2S是一种废气资源化的有效手段。     

用电化学氧泵调节氧含量测定TOD的方法

采用高温催化氧化、电化学氧泵供氧、半导体致冷、高温固体电解质检测器等新技术测定 TOD,具有氧化效率高、氧量稳定可调、除湿效果好、检测范周广、灵敏度高等特点。该法可为废水处理工艺控制及环境水质监测提供综合性的分析数据。     

化学沉淀与高级氧化法处理乙烯裂解废碱液的研究

采用化学沉淀与高级氧化(UV／H2O2)法去除乙烯裂解废碱液中的硫化物及有机物。考察了影响效果的各种因素。试验结果表明：化学沉淀在反应温度为20℃、反应时间为30min、CuO与Na2S的摩尔比为1．45：1;高级氧化反应温度为40℃、反应时间为120min、H2O2的加入量(H202／COD质量比)为0．8的条件下,废碱液中S^2-的去除率可达98％以上,COD总去除率可达87％,BOD5／COD由处理前的0．21提高至0．54。     

新型高级氧化技术处理硫化染料废水的研究进展

综述了各种用于硫化染料废水的新型高级氧化技术,包括电化学氧化法、E-peroxone氧化法、类Fenton试剂氧化法、光催化氧化法、光催化与膜分离耦合法和光催化燃料电池法。分析了各种高级氧化技术的主要影响因素,并指出各种方法的优势与不足,对高级氧化技术的发展方向提出了展望,为今后硫化染料废水的综合治理提供了技术指导。     

铁离子湿式氧化法脱除硫化氢技术进展

综述了铁离子湿式氧化脱除H2S技术的起源及其各种方法的原理和特点。H2S的脱除速度与副反应抑制、铁离子的稳定性和再生速度是各种技术应用与改进的关键因素。生化铁一碱溶液催化脱硫方法是气体脱硫值得发展的方向。     

制药废水生化出水的强化混凝—高级氧化深度处理组合工艺比较

采用强化混凝和高级氧化法对制药废水生化出水进行深度处理,比较了不同混凝剂、不同氧化方法(包括Na2S2O8氧化、电化学氧化、Fenton/类Fenton氧化)的处理效果.实验结果表明:经聚合硫酸铁与聚丙烯酰胺强化混凝处理后,废水的COD去除率达18.5％;强化混凝与不同氧化方法联用均可使废水脱色至无色,COD去除率达7...     

蒽醌修饰石墨毡电极预处理头孢合成废水

以钛涂钌电极为阳极、自制蒽醌修饰石墨毡电极为阴极,对头孢合成废水(COD=25 000~30 000 mg/L、ρ(NH3-N)=850~1 300 mg/L、色度为2 300~2 680度)进行了电化学氧化预处理,优化了电解条件,并对电化学体系的动力学和稳定性进行了分析。实验结果表明:蒽醌的存在可改善电化学氧化降解效果;在电解时间50 min、电流密度0.14 A/cm2、Na2SO4浓度0.1 mol/L、极板间距2 cm、初始废水p H 7.0的条件下,废水的COD、色度、NH3-N的去除率分别可达45.3%,66.9%,33.6%;BOD5/COD由处理前的0.27增至0.40,可生化性得到改善;COD、色度、NH3-N的电化学氧化降解过程均近似符合一级动力学方程;且该电化学体系的应用稳定性良好。     

活性炭纤维电极法烟气脱硫研究

用活性炭纤维做电极,对烟气进行吸附氧化脱硫研究。探讨了活性炭纤维电极的吸附性能及化学氧化过程中SO2的转化规律。试验表明,活性炭纤维电极具有良好的导电性与吸附性,脱硫率达到95％,其中77％的SO2经电化学氧化为硫酸,同时这一过程可使活性炭纤维再生,延长其使用周期。     

电化学法回收废碱液

安格尔(Ангарский)国立技术研究所采用电化学法回收废碱液,废碱液组成为：游离碱1%-3.5%(质量分数),化合碱2%-5.75%(质量分数),亚硫酸盐和硫代硫酸盐1.5%-4%(质量分数),总钠3-10 g/L(质量浓度),此外,还含有少量环烷酸盐、酚盐、碳酸盐、乳化油、悬浮物等。 　　试验在电解槽中进行,可以选用Pt、Ti/Pt、Pb/PbO2、Ti/PbO2、Ti/MnO2等作电极材料。具体反应如下： 　　阴极：2H2O+4e→2OH-+H2↑ 　　阳极：2H2O-4e→4H++O2↑ 　　　　　2OH--4e→2H++O2↑ 　　　　　S2--2e→S↓ 　　　　　S2-+4H2O+8e→SO42-+8H+ 　　电解液：2S2-+O2+2OH-→S2O32-+H2O 　　　　　　2S2O32-+6H+→SO32-+3S↓+3H2O 　　　　　　S2-+2H+→H2S↑ 　　同时还发生硫醇、噻吩、酚、环烷酸盐等含硫有机物的氧化反应。 　　电解槽中有多孔石棉隔膜和钢网阴极,电流强度为5-40 A。选择良好的阳极材料对阳极反应有电催化作用,可以促进生成结晶硫或硫酸盐。增加阳极电流密度(ia)可以提高硫代硫酸盐的转化率,当ia＞400 A/m2时,硫代硫酸盐的转化率接近100%,酚的转化率达到87%-95%。连续电解1000 h,可使产碱率超过90%,单位电能损耗不超过4000 kVT．h/t(NaOH),电解装置电压4.5-5.5 V,回收液的游离碱度为6%-12%(以NaOH计)。进一步研究证明,利用膜法电解可以改善回收碱液的组分,并可将其中NaOH的质量分数提高到20%-30%。     

废水中难降解有机物的高级氧化技术

综述了近年来废水难降解有机污染物的高级氧化处理技术,主要包括化学氧化、电化学氧化、湿空气氧化、超临界水氧化及光催化氧化技术等。介绍了各种处理技术的基本原理及研究进展,并对其特点进行了评述。     

Energy recovery from solid waste fuels using advanced gasification technology

Since the mid-1980s, TPS Termiska Processer AB has been working on the development of an atmospheric-pressure gasification process. A major aim at the start of this work was the generation of fuel gas from indigenous fuels to Sweden (i.e. biomass). As the economic climate changed and awareness of the damage to the environment caused by the use of fossil fuels in power generation equipment increased, the aim of the development work at TPS was changed to applying the process to heat and power generation from feedstocks such as biomass and solid wastes. Compared with modern waste incineration with heat recovery, the gasification process will permit an increase in electricity output of up to 50%. The gasification process being developed is based on an atmospheric-pressure circulating fluidised bed gasifier coupled to a tar-cracking vessel. The gas produced from this process is then cooled and cleaned in conventional equipment. The energy-rich gas produced is clean enough to be fired in a gas boiler (and, in the longer term, in an engine or gas turbine) without requiring extensive flue gas cleaning, as is normally required in conventional waste incineration plants. Producing clean fuel gas in this manner, which facilitates the use of efficient gas-fired boilers, means that overall plant electrical efficiencies of close to 30% can be achieved. TPS has performed a considerable amount of pilot plant testing on waste fuels in their gasification/gas cleaning pilot plant in Sweden. Two gasifiers of TPS design have been in operation in Grève-in-Chianti, Italy since 1992. This plant processes 200 tonnes of RDF (refuse-derived fuel) per day. It is planned that the complete TPS gasification process (including the complete fuel gas cleaning system) be demonstrated in several gas turbine-based biomass-fuelled power generating plants in different parts of the world. It is the aim of TPS to prove, at commercial scale, the technical feasibility and economic advantages of the gasification process when it is applied to solid waste fuels. This aim shall be achieved, in the short-term, by employing the cold clean product gas in a gas boiler and, in the longer-term, by firing the gas in engines and gas turbines. A study for a 90 MWth waste-fuelled co-generation plant in Sweden has shown that, already today, gasification of solid waste can compete economically with conventional incineration technologies.     

Technical assessment of fuel cell operation on anaerobic digester gas at the Yonkers, NY, wastewater treatment plant

This paper summarizes the results of a 2-year field test to assess the performance of a specially modified commercial phosphoric acid 200-kW fuel cell power plant to recover energy from anaerobic digester gas (ADG) which has been cleansed of contaminants (sulfur and halide compounds) using a patented gas pretreatment unit (GPU). Specific project goals include characterization of the fuel cell power plant emissions and verification of the GPU performance for removing sulfur contaminants. To remove halide contaminants from the ADG, a halide guard, consisting of a vessel with a metal oxide supported on alumina, was incorporated into the fuel cell reactant supply. This first-of-a-kind demonstration was conducted at the Yonkers, NY, wastewater treatment plant, a sewage processing facility owned and operated by Westchester County. Results have demonstrated that the ADG fuel cell power plant can produce electrical output levels close to full power (200 kW) with negligible air emissions of CO, NO(x), and SO(2). The GPU removed virtually 100% of H(2)S and 88% of organic sulfur, bringing the overall sulfur removal efficiency of the GPU to over 99%. The halide guard removed up to 96% of the halides exiting the GPU.     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 2000     

Removal of H2S using molten carbonate at high temperature

Gasification is considered to be an effective process for energy conversion from various sources such as coal, biomass, and waste. Cleanup of the hot syngas produced by such a process may improve the thermal efficiency of the overall gasification system. Therefore, the cleanup of hot syngas from biomass gasification using molten carbonate is investigated in bench-scale tests. Molten carbonate acts as an absorbent during desulfurization and dechlorination and as a thermal catalyst for tar cracking. In this study, the performance of molten carbonate for removing H₂S was evaluated. The temperature of the molten carbonate was set within the range from 800 to 1000 °C. It is found that the removal of H₂S is significantly affected by the concentration of CO₂ in the syngas. When only a small percentage of CO₂ is present, desulfurization using molten carbonate is inadequate. However, when carbon elements, such as char and tar, are continuously supplied, H₂S removal can be maintained at a high level.To confirm the performance of the molten carbonate gas-cleaning system, purified biogas was used as a fuel in power generation tests with a molten carbonate fuel cell (MCFC). The fuel cell is a high-performance sensor for detecting gaseous impurities. When purified gas from a gas-cleaning reactor was continuously supplied to the fuel cell, the cell voltage remained stable. Thus, the molten carbonate gas-cleaning reactor was found to afford good gas-cleaning performance.     

硫酸盐对微生物燃料电池脱氮的影响

构建了双室型微生物燃料电池(MFC),探讨了硫酸盐对MFC阴极脱氮效果和产电性能的影响。实验结果表明:缺氧阴极室中,硝酸盐氮、硫酸盐的还原存在一定的竞争关系,且硫酸盐对电子的竞争能力比硝酸盐氮强;当S与N的质量比(记为S/N)为2∶1时,72 h后的硫酸根去除率达96.41%,而硝酸盐氮去除率仅为36.86%;在S/N为2∶1的条件下,当电压达307.6 m V时,功率密度达最大值15.77 W/m2,电池内阻为100Ω,与未加入硫酸盐时相比产电性能明显提高。     

火电厂燃煤烟气过氧化氢脱硝技术的研究及应用

H2O2脱硝工艺是面向火电厂烟气污染物控制的一种环境友好型控制技术。通过对H2O2脱硝反应机理、关键影响因素、工艺路线和经济性等方面研究,综述了国内外H2O2脱硝技术研究进展,分析了不同工艺中存在的问题,并针对存在的问题进行了探讨。     

Gasification applicability study of polyurethane solid refuse fuel fabricated from electric waste by measuring syngas and nitrogenous pollutant gases

To recycle polyurethane foam waste generated from electric appliance recycling centers for use as fuel in a gasification process, polyurethane solid refuse fuel fabricated as pellets was analyzed for the characteristics of elemental composition, proximate analysis, heating value, and thermo-gravimetric testing. It has a high heating value of 29.06 MJ/kg with a high content of combustibles, which could be feasibly used in any thermal process. However, the nitrogen content, of up to 7 %, was comparably higher than for other fuels such as coal, biomass, and refuse-derived fuel, and may result in the emission of nitrogenous pollutant gases of HCN and NH₃. By conducting gasification experiments on polyurethane solid refuse fuel in a fixed-bed reactor, a syngas with a heating value of 9.76 kJ/m³ and high content of both H₂ and CO were produced with good gasification efficiency; carbon conversion 54 %, and cold gas efficiency 60 %. The nitrogenous pollutant gases in syngas were measured at the concentrations of 160 ppm hydrogen cyanide and 40 ppm ammonia, which may have to be reduced using proper cleaning technologies prior to the commercialization of gasification technology for polyurethane waste.     

Molten carbonate fuel cells fed with biogas: Combating H2S

The use of biomass and waste to produce alternative fuels, due to environmental and energy security reasons, is a high-quality solution especially when integrated with high efficiency fuel cell applications. In this article we look into the coupling of an anaerobic digestion process of organic residues to electrochemical conversion to electricity and heat through a molten carbonate fuel cell (MCFC). In particular the pathway of the exceedingly harmful compound hydrogen sulphide (H₂S) in these phases is analysed. Hydrogen sulphide production in the biogas is strongly interrelated with methane and/or hydrogen yield, as well as with operating conditions like temperature and pH. When present in the produced biogas, this compound has multiple negative effects on the performance and durability of an MCFC. Therefore, there are important issues of integration to be solved.Three general approaches to solve the sulphur problem in the MCFC are possible. The first is to prevent the formation of hydrogen sulphide at the source: favouring conditions that inhibit its production during fermentation. Secondly, to identify the sulphur tolerance levels of the fuel cell components currently in use and develop sulphur-tolerant components that show long-term electrochemical performance and corrosion stability. The third approach is to remove the generated sulphur species to very low levels before the gas enters the fuel cell.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

Assessment of mobility and bioavailability of contaminants in MSW incineration ash with aquatic and terrestrial bioassays

Incineration of municipal solid waste (MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction as well as a source of renewable energy. In the process fly and bottom ash is generated as a waste material. The ash residue may vary greatly in composition depending on the type of waste incinerated and it can contain elevated levels of harmful contaminants such as heavy metals. In this study, the ecotoxicity of a weathered, untreated incineration bottom ash was characterized as defined by the H14 criterion of the EU Waste Framework Directive by means of an elemental analysis, leaching tests followed by a chemical analysis and a combination of aquatic and solid-phase bioassays. The experiments were conducted to assess the mobility and bioavailability of ash contaminants. A combination of aquatic and terrestrial bioassays was used to determine potentially adverse acute effects of exposure to the solid ash and aqueous ash leachates. The results from the study showed that the bottom ash from a municipal waste incineration plant in mid-Sweden contained levels of metals such as Cu, Pb and Zn, which exceeded the Swedish EPA limit values for inert wastes. The chemical analysis of the ash leachates showed high concentrations of particularly Cr. The leachate concentration of Cr exceeded the limit value for L/S 10 leaching for inert wastes. Filtration of leachates prior to analysis may have underestimated the leachability of complex-forming metals such as Cu and Pb. The germination test of solid ash and ash leachates using T. repens showed a higher inhibition of seedling emergence of seeds exposed to the solid ash than the seeds exposed to ash leachates. This indicated a relatively low mobility of toxicants from the solid ash into the leachates, although some metals exceeded the L/S 10 leaching limit values for inert wastes. The Microtox® toxicity test showed only a very low toxic response to the ash leachate exposure, while the D. magna immobility test showed a moderately high toxic effect of the ash leachates. Overall, the results from this study showed an ecotoxic effect of the solid MSW bottom ash and the corresponding ash leachates. The material may therefore pose an environmental risk if used in construction applications. However, as the testing of the solid ash was rather limited and the ash leachate showed an unusually high leaching of Cr, further assessments are required in order to conclusively characterize the bottom ash studied herein as hazardous according to the H14 criterion.