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.     

湿法烟气脱硫环境下亚硫酸钙强制催化氧化的研究

采用机械搅拌槽式反应器,对湿法烟气脱硫环境进行模拟以研究锰催化对亚硫酸钙氧化的影响。实验得出:湿法烟气脱硫环境下,当槽内亚硫酸钙浆液浓度很小时,锰离子催化氧化对SIV浓度是1.5级,对Mn2+浓度是0.5 级;随着亚硫酸钙浆液增加至某一浓度后,氧化反应开始遵循并行反应机理,即氧化反应包括SIV离子的非催化氧化反应和SIV离子的锰离子催化氧化反应,且锰离子的催化氧化反应对Mn2+浓度是0.5级。文中提出的氧化反应速率的试验公式可以用来对湿法烟气脱硫中的氧化过程进行模拟。     

煤浆催化氧化法烟气脱硫研究

基于液相催化氧化原理,以煤浆做洗涤介质进行烟气脱硫。此法起催化作用的Fe2+/Fe3+离子通过SO2、O2和煤中的黄铁矿作用而现场产生。实验过程控制模拟烟气中的SO2摩尔分率和O2浓度范围分别为760×10-6￣3200×10-6和3%￣20%。实验表明,反应温度约在40℃以上时,脱硫率即达90%以上。二氧化硫浓度增大,脱硫率呈下降趋势,与石灰/石灰石脱硫过程类似。在实验范围内,pH值和氧气浓度对脱硫率基本没有影响,实际烟气中的O2浓度完全满足催化氧化反应的需要。随烟气脱硫过程的进行,脱硫浆液中的总铁含量不断增加,说明煤中黄铁矿被不断浸出,故此法在脱除烟气中的二氧化硫的同时也降低了煤中的黄铁矿硫。     

蒸汽相变促进WFGD系统脱除PM_(2.5)的协同作用分析

蒸汽相变作为预处理措施能显著提高常规除尘设备对PM2.5细颗粒的脱除效率,但对于水汽含量低的原始燃煤烟气蒸汽耗量太大,限制了工程应用,而在燃煤电厂湿法烟气脱硫(WFGD)过程中,烟气降温增湿,再添加少量蒸汽就可以建立PM2.5凝结长大所需要的过饱和环境,进而实现WFGD系统对PM2.5的协同高效脱除。在分析蒸汽相变促进PM2.5脱除影响因素的基础上,结合湿法脱硫过程传热传质特性,定性分析了脱硫塔塔前、塔内和塔出口添加蒸汽对WFGD系统脱除PM2.5的促进作用,并提出具体工艺方案。     

石灰湿法脱硫传质－反应过程机理

对以族流板塔作吸收器的石灰湿法烟气脱硫技术进行了试验研究,分析了石灰浆液吸收ＳＯ２的传质－反应过程,并提出了Ｃａ（ＯＨ）２浆液吸收ＳＯ２的传质－反应过程机理。本机理认为,总反应速度由气相中ＳＯ２的扩散（气相阻力）和液相中Ｃａ（ＯＨ）２固体的溶解（包括在液相阻力之内）及扩散控制;同时认为,反应过程可分为气相阻力控制、气液相阻力共同控制、液相阻力控制３个阶段。此外,本机理得到了实验的验证。以上结果将有助于改进石灰湿法烟气脱硫工业装置的设计和操作。     

电石渣中杂质对亚硫酸钙氧化及石膏浆液脱水性能影响

为了考察电石渣中杂质(Na2S、SiO2及铁、镁、铝的氧化物等)在湿法烟气脱硫过程中对亚硫酸钙氧化及石膏浆液脱水性能的影响,通过建立亚硫酸钙氧化反应装置,对亚硫酸钙氧化及石膏浆液脱水过程进行了研究。研究表明:浆液中Na2S浓度越高,亚硫酸钙氧化受到的抑制作用越明显,Na2S浓度高于10.0 mmol/L时,浆液中亚硫酸根几乎不发生氧化反应,石膏平均粒径随Na2S浓度增加呈先降低后增大趋势。浆液中SiO2不影响亚硫酸钙氧化,但是浓度低于0.5 g/L时,石膏粒径分布更加集中,更有利于提高石膏浆液脱水性能。浆液中Fe2O3的存在有利于亚硫酸钙氧化,浓度在0.5～1.0 g/L时,对石膏浆液脱水性能有明显的改善作用。浆液中MgO、Al2O3的存在,对亚硫酸钙氧化影响不大,但降低了石膏浆液脱水性能。     

石灰湿法脱硫传质－反应过程机理

对以旋流板塔作吸收器的石灰湿法烟气脱硫技术进行了试验研究。分析了为浆液吸收ＳＯ２的传质－反应过程，并提出了Ｃａ（ＯＨ）２浆液吸收ＳＯ２的传质－反应过程机理。本机理认为，总反应速度由气相中ＳＯ２的扩散（气相阻力）和液相中Ｃａ（ＯＨ）２固体的溶解（包括在液相阻力之内）及扩散控制；同时认为，反应过程可分为气相阻力控制、所液共同控制、液相阻力控制３个阶段。此外，本机得到了实验的验证。以上结果将有助于改进为     

氨法脱硫反应特性的化学动力学分析

对采用氨法脱除烟气中SO2过程的反应特性进行了热力学和动力学分析．结果显示,氨法脱硫反应活化能较低,只要温度控制适当,氨法脱硫具有很高的平衡常数(或转化率)和良好的动力学特性．同时,根据实验结果拟合整理出了实验温度范围内氨法脱硫反应的Arrhenius方程,分析了温度对氨法脱硫反应速率的具体影响．     

控制氧化对湿法烟气脱硫过程的影响研究

在喷射鼓泡反应器上进行了控制氧化对湿法烟气脱硫过程的影响研究,测定了脱硫率η和pH随时间t的变化规律,得出了η与t的回归式及η与pH值的关系规律,讨论了不同曝气强度及抑制剂浓度对CaCO3利用率α、pH值及脱硫率η的影响。实验表明强制氧化及抑制氧化均能提高脱硫效率η及CaCO3利用率α,但对浆液pH值的影响正好相反,强制氧化使浆液pH值下降的更快,而抑制氧化则使浆液pH值有所提高。     

烟气脱硫过程中添加剂对石灰石的促溶作用

以双搅拌釜为实验设备,研究了烟气脱硫过程中硫酸钠、硫酸镁和腐殖酸钠对石灰石的促溶作用.结果表明,分别采用3种不同添加剂时,pH值等随脱硫反应时间的变化规律类似;与非强化石灰石脱硫过程对比,在相同pH值下,3种添加剂均使石灰石颗粒体积占初始体积的分率rp减小,即均能促进石灰石的溶解,改善浆液的传质性能.通过理论分析,导出了r_p与浆液pH值之间的关系式,该方程能很好地关联双搅拌釜实验数据.     

Effect of calcium formate as an additive on desulfurization in power plants

SO_2 in flue gas needs to be eliminated to alleviate air pollution. As the quality of coal decreases and environmental standard requirements become more stringent, the highefficiency desulfurization of flue gas faces more and more challenges. As an economical and environmentally friendly solution, the effect of calcium formate as an additive on desulfurization efficiency in the wet flue gas desulfurization(WFGD) process was studied for the first time. Improvement of the desulfurization efficiency was achieved with limited change in p H after calcium formate was added into the reactor, and it was found to work better than other additives tested. The positive effects were further verified in a power plant, which showed that adding calcium formate could promote the dissolution of calcium carbonate, accelerate the growth of gypsum crystals and improve the efficiency of desulfurization. Thus, calcium formate was proved to be an effective additive and can potentially be used to reduce the amount of limestone slurry required, as well as the energy consumption and operating costs in industrial desulfurization.     

废水处理中湿式氧化技术研究进展

综述了湿式氧化技术的特点，影响因素、反应机理和动力学，并就其在废水处理中的研究和应用现状，指出湿式氧化是在处理高浓度难降解有机有害废水中较有发展前任的技术。     

燃煤烟气脱硫技术分析

介绍了国内目前正在使用或即将使用的燃煤烟气脱硫技术的工艺特点、操作参数和适用范围。这些技术包括湿式石灰石(石灰)-石膏法、炉内喷钙后部烟气增湿脱硫法、海水洗涤法、除尘脱硫一体化技术等。     

Simultaneous removal of CO2, NOx and SOx using single stage absorption column

Capturing flue gases often require multiple stages of scrubbing, increasing the capital and operating costs. So far, no attempt has been made to study the absorption characteristics of all the three gases (NO, SO₂ and CO₂) in a single stage absorption unit at alkaline pH conditions. We have attempted to capture all the three gases with a single wet scrubbing column. The absorption of all three gases with sodium carbonate solution promoted with oxidizers was investigated in a tall absorption column. The absorbance was found to be 100% for CO₂, 30% for NO and 95% for SO₂ respectively. The capture efficiency of sodium carbonate solution was increased by 40% for CO₂ loading, with the addition of oxidizer. Absorption kinetics and reaction pathways of all the three gases were discussed individually in detail.     

铁屑置换沉淀海绵铜动力学研究

从动力学角度研究了铁屑置换沉淀海绵铜的化学反应机理,探讨了溶液pH,Cu2+初始浓度,振荡强度和温度等因素对铜置换率的影响及动力学模型。通过测定不同温度条件下的表观反应速率常数(k);求得置换反应活化能为16.21kJ/mol。试验结果表明,置换反应的所有动力学数据服从一级反应速率规律,置换过程符合扩散控制机理。     

氨法脱硫工艺S(IV)氧化动力学模型研究

目前,有关氨法脱硫技术对S(IV)氧化的研究未考虑HSO-3及离子强度等因素的影响.因此,本文根据氨法脱硫反应机理建立实验装置对S(IV)氧化动力学进行了研究,考察了SO2-3浓度、SO2-4浓度、pH值、温度和氧化空气量对S(IV)氧化速率的影响.结果表明,S(IV)的氧化速率与SO2-3浓度呈-0.5级关系,与SO2-4浓度之间的关系为r(IV)=0.00121exp(-0.89CSO2-4);HSO-3较SO2-3更容易被氧化,保持较低pH值时对S(IV)的氧化有利;S(IV)的氧化速率随氧化空气量和温度的升高而增大,反应的表观活化能约为28.0 kJ·mol-1.利用数学模型对S(IV)氧化过程进行了数值模拟,结果表明,该模型能够较好地反映氨法脱硫S(IV)氧化过程.     

Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

Four metal oxide catalysts composed of copper (Cu), stannum (Sn), copper-stannum (Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al2O3 ) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu-10% Ce/γ-Al2 O3 showed the best catalytic activity. This is consistent witht he result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 rain. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.     

SO32-活化S2O82-降解偶氮染料废水的机制研究

为深度处理偶氮染料废水,以甲基橙（MO）为目标污染物,研究了亚硫酸盐活化过硫酸盐产活性物种的新型高级氧化处理方法,并对活化机制、氧化机理及动力学理论进行分析.通过对SO₃^2-/S₂O₈^2-,S₂O₈^2-,SO₃^2-3种体系进行降解对比和ESR等技术表征对比,发现亚硫酸盐能显著活化过硫酸根产生硫酸根自由基,其能氧化破坏MO偶氮双键形成的共轭体系,有较好的脱色降解效果.考察了亚硫酸盐和过硫酸盐摩尔比、过硫酸盐投加量、初始pH值对降解效果的影响,结果表明当初始pH值为3.0,摩尔比1：1,投加量为20.0mmol/L、反应时间在300min下对MO降解率能达到96.1%,进一步发现该体系对初始pH值的适应范围较广（3.0~11.0）.基于Box-behnken设计的响应面模拟和方差分析得到了可达显著水平的二次响应曲面模型,影响因子对MO降解的贡献排序为：过硫酸盐投加量 > 初始pH值 > 摩尔比.初始MO浓度动力学分析发现不同初始浓度下对MO的降解过程遵循准二级反应动力学规律,反应动力学常数从1.8212×10^-4~2.4649×10^-4min^-1.另一方面发现升高反应温度可以促进体系对MO的降解,根据不同温度下活化过程的反应速率常数的阿累尼乌斯准二级反应的活化能计算结果（E_a=44.9kJ/mol）,发现其相比常规金属活化方式较低,因此该体系对有毒有害的工业有机废水处理有潜在的商业应用价值.     

石灰石脱硫反应活性的研究

脱硫剂石灰石的反应活性对流化床燃煤锅炉的脱硫效果影响很大。目前,国内外主要采用动力学方法,通过测定固态CaO的硫酸盐化程度来推断石灰石的反应活性。但是这在石灰石中含有许多其它杂质成分时是不够全面的,因为这些杂质成分对石灰石的脱硫反应活性影响很大,不能忽视。为此,通过测定流化床入口和出口的SO₂浓度变化来判断加入床中的石灰石样品的反应活性。由于凡是能引起SO₂浓度变化的物质都与石灰石的反应活性有关,从而克服了原有方法仅考虑CaO重量变化的片面性。本文也采用了动力学方法建立了石灰石反应动力学模型,并利用线性化方法对其反应速率常数Ｋ进行线性估计,建立了石灰石化学成分与活性关系的数学模型。     

Treatment of desizing wastewater from the textile industry by wet air oxidation

This paper describes the application of wet air oxidation to the treatment of desizing wastewater from two textile companies. A two-liter high temperature, high pressure autoclave reactor was used in the study. The range of operating temperatures examined was between 150 and 290℃, and the partial pressure of oxygen ranged from 0. 375 to 2.25 MPa. Variations in pH,CODCr and TOD content were monitored during each experiment and used to assess the extent of conversion of the process. The effects of temperature, pressure and reaction time were explored extensively. More than 90 ％ CODCr reduction and 80 ％ TOC removal have been obtained. The results have also been demonstrated that WAO is a suitable pre-treatment methods due to improvement of the BOD5/CODCr ratio of desizing wastewater. The reaction kinetics of wet air oxidation of desizing wastewater has been proved to be two steps, a fast reaction followed by a slow reaction stage.