钙法烟气脱硫技术研究进展

综述了湿法、干法与半干法3种钙法烟气脱硫技术的主要特点、脱硫机理及主要影响因素。对3种方法在脱硫过程中出现的问题进行了分析并提出了相应的对策。     

Control of mercury vapor emissions from combustion flue gas

GOAL, SCOPE AND BACKGROUND: Mercury (Hg) emission from combustion flue gas is a significant environmental concern due to its toxicity and high volatility. A number of the research efforts have been carried out in the past decade exploiting mercury emission, monitoring and control from combustion flue gases. Most recently, increasing activities are focused on evaluating the behavior of mercury in coal combustion systems and developing novel Hg control technologies. This is partly due to the new regulatory requirement on mercury emissions from coal-fired combustors to be enacted under the U.S. Title III of the 1990 Clean Air Act Amendments. The aim of this review work is to better understand the state-of-the-art technologies of flue gas mercury control and identify the gaps of knowledge hence areas for further opportunities in research and development. MAIN FEATURES: This paper examines mercury behaviors in combustion systems through a comprehensive review of the available literature. About 70 published papers and reports were cited and studied. RESULTS AND DISCUSSION: This paper summarizes the mechanisms of formation of mercury containing compounds during combustion, its speciation and reaction in flue gas, as well as subsequent mobilization in the environment. It also provides a review of the current techniques designed for real-time, continuous emission monitoring (CEM) for mercury. Most importantly, current flue gas mercury control technologies are reviewed while activated carbon adsorption, a technology that offers the greatest potential for the control of gas-phase mercury emissions, is highlighted. CONCLUSIONS AND RECOMMENDATIONS: Although much progress has been achieved in the last decade, techniques developed for the monitoring and control of mercury from combustion flue gases are not yet mature and gaps in knowledge exist for further advancement. More R&D efforts are required for the effective control of Hg emissions and the main focuses are identified.     

低温等离子强化复合钙基吸附剂脱汞实验研究

在固定床吸附实验台上对低温等离子改性前后的复合钙基吸附剂进行脱汞实验,深入探究SO₂和O₂对具有较高孔隙率和比表面积的复合钙基吸附剂脱汞性能的影响.并通过多种表征手段和方法分析复合钙基吸附剂对Hg⁰的吸附机理.实验结果表明,由于等离子改性提高了吸附剂表面的含氧官能团的相对含量,经等离子改性的复合钙基吸附剂的脱汞效率有明显提高.在N₂+0.07% SO₂+6% O₂气氛下,吸附剂脱汞效率相比于无氧气氛由23.7%增至91.2%,吸附剂脱汞效率明显提高.此时吸附剂表面的羟基、酯基官能团作为主要反应活性位点,而羰基官能团的作用不明显.O₂的存在促使活性炭表面由碳原子不饱和键形成的活性位增加,促进了Hg⁰的吸附,同时生成多种汞化合物.随着SO₂浓度升至0.15%,改性复合钙基吸附剂表面活性位再次出现不足,此时SO₂抢夺Hg⁰的吸附位点,脱汞效率降至23.3%.     

燃煤烟气同时脱硫脱硝机理概述

按机理的不同,将烟气同时脱硫脱硝技术分为两大类。较全面的介绍了目前有代表性的同时脱硫脱硝技术的机理和特点。认为同时脱硫脱硝技术相比于单独脱硫脱硝具有良好的经济性和灵活的技术选择性。其中以钙基吸附剂为主体的常温干法/半干法同时脱硫脱硝技术,有低成本、脱除产物易处置、不用水或少用水等特点,是适合我国国情的一项燃煤污染防治技术。     

Removal of elemental mercury by iodine-modified rice husk ash sorbents

Iodine-modified calcium-based rice husk ash sorbents(I2/CaO/RHA) were synthesized and characterized by X-ray diffraction,X-ray fluorescence,and N2 isotherm adsorption/desorption.Adsorption experiments of vapor-phase elemental mercury(Hg0) were performed in a laboratory-scale fixed-bed reactor.I2/CaO/RHA performances on Hg0 adsorption were compared with those of modified Ca-based fly ash sorbents(I2/CaO/FA) and modified fly ash sorbents(I2/FA) .Effects of oxidant loading,supports,pore size distribution,iodine impregnation modes,and temperature were investigated as well to understand the mechanism in capturing Hg0.The modified sorbents exhibited reasonable effciency for Hg0 removal under simulated flue gas.The surface area,pore size distribution,and iodine impregnation modes of the sorbents did not produce a strong effect on Hg0 capture effciency,while fair correlation was observed between Hg0 uptake capacity and iodine concentration.Therefore,the content of I2 impregnated on the sorbents was identified as the most important factor influencing the capacity of these sorbents for Hg0 uptake.Increasing temperature in the range of 80-140°C caused a rise in Hg0 removal.A reaction mechanism that may explain the experimental results was presumed based on the characterizations and adsorption study.     

Catalytic oxidation of calcium sulfite in solution/aqueous slurry

Forced oxidation of calcium sulfite aqueous slurry is a key step for the calcium-based flue gas desulfudzation(FGD) residue.Experiments were conducted in a semi-batch system and a continuous flow system on lab scales. The main reactor in semi-batch system is a 1000 ml volume flask. It has five necks for continuous feeding of gas and a batch of calcium sulfite solution/aqueous slurry. In continuous flow system, the main part is a jacketed Pyrex glass reactor in which gas and solution/aqueous slurry are fed continuously.Calcium sulfite oxidation is a series of complex free-radical reactions. According to experimental results and literature data, the reactions are influenced significantly by manganese as catalyst. At low concentration of manganese and calcium sulfite, the reaction rate is dependent on 1.5 order of sulfite concentration, 0.5 order of manganese concentration, and zero order of oxygen concentration in which the oxidation is controlled by chemical kinetics. With concentrations of calcium sulfite and manganese increasing, the reactions are independent gradually on the constituents in solution but are impacted by oxygen concentration. Manganese can accelerate the free-radical reactions, and then enhances the mass transfer of oxygen from gas to liquid. The critical concentration of calcium sulfite is 0.007 mol/L,manganese is 10^-4 mol/L, and oxygen is of 0.2-0.4 atm.     

简易干法烟气脱硫技术的试验研究

为了开发研究低投资,低成本的脱硫方法,在研制高活性多孔脱硫剂的过程中,研究了各种因素的影响,并对脱硫剂进行物化特性的表征。脱硫剂比表面积可达４１ｍ＾２／ｇ,粒径分布：０－１μｍ占２４．１％．－１０－２０μｍ占２０．１％;２０－４０μｍ占２９．０％,４０μｍ－６０μｍ占１０．３％。实验室小试,用固定床反应器模拟研究干法烟气脱硫反应过程,烟气相对湿度,脱硫剂比表面积,反应温度等为影响脱硫剂与ＯＳ２反应     

Fe_2O_3和K_2CO_3对钙基添加剂脱硫脱硝的影响

在研究焦炭燃烧过程中使用钙基添加剂固硫的基础上,探讨了Fe_2O_3或K_2CO_3对CaO脱硫脱硝的影响。实验结果表明:添加剂的种类对焦炭燃烧过程中排放的SO_2和NO的浓度及总量均有一定的影响;加入Fe_2O_3或K_2CO_3替代部分CaO后,焦炭燃烧过程中排放的SO_2和NO比单独加入CaO时均有所下降;向焦炭中分别混合3.0%(w)CaO),1.5%(w)CaO+1.5%(w)Fe_2O_3,1.5%(w)CaO+1.5%(w)K_2CO_3的添加剂时,焦炭的SO_2排放总量分别降低了69.93%,75.98%,79.98%,NO排放总量分别降低了64.38%,79.73%,84.14%;加入Fe_2O_3或K_2CO_3后,钙基添加剂的表面性质发生了变化,同时增加了反应的活性中心数,因而复合添加剂能更有效地进行脱硫脱硝。     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

用于干式脱污的CaO蒸汽活化实验研究

利用小型活化转炉实验台对以CaO为主要成分的钙基脱污剂在300～650℃的温度范围内进行蒸汽活化处理,结合X射线衍射和压汞仪的分析结果,初步探讨了蒸汽活化的机理.研究表明,蒸汽活化温度在600℃以上时,脱污剂孔隙结构有显著的改善,比孔容积和比表面积有着显著的增加,微孔（＜100nm）的数量大量增加,而低温下蒸汽活化的效果不是十分明显;研究还发现高温下延长活化时间有利于改善脱污剂的孔隙结构.