Electron beam process for SO2 removal from flue gases with high SO2 content

Flue gases with high SO₂ concentration are emitted from different industrial processes, e.g. combustion of coal with high sulfur content, copper smelting and sintering plant. The application of the electron beam process for SO₂ removal from such flue gases was investigated. A parametric study was carried out to determine the removal efficiency as a function of temperature and humidity of irradiated gases, dose and ammonia stoichiometry. At the dose 11.5 kGy 95% SO₂ removal efficiency was obtained when the temperature and humidity of irradiated flue gases and ammonia stoichiometry were properly adjusted. The synergistic effect of high SO₂ concentration on NO_x removal was observed. The collected by-product was the mixture of (NH₄)₂ SO₄ and NH₄NO₃. The content of heavy metals in the by-product was many times lower than the values acceptable for commercial fertilizer.     

Kinetics of SO2 removal from flue gas by electron beam technique

Laboratory scale experiments were carried out in order to get more information about the oxidation of SO₂ by OH radicals (homogeneous reaction) and the oxidation of SO₂ at aerosol surfaces (heterogeneous reaction). For the experiment of homogeneous reaction, SO₂ was added to synthetic flue gas without initial NO and without ammonia and the mixture was irradiated with electron beam. The SO₂ removal was measured as a function of temperature and water vapour concentration at constant dose. For the experiment of heterogeneous reaction, SO₂ was added to nucleating sulfuric acid aerosol. No SO₂ removal was observed in this case. So, it can be concluded that the heterogeneous oxidation of SO₂ is negligible in the absence of ammonia. Therefore, the oxidation of SO₂ must be interpreted merely by homogeneous gas phase chemistry. The gas phase kinetics are derived from comparison of experimental results and computer modelling.     

应用水汽相变促进湿法脱硫净烟气中PM_(2.5)和SO_3酸雾脱除的研究

在石灰石-石膏法脱硫净烟气中分别采用添加适量蒸汽和湿空气方式建立PM_(2.5)和SO_3酸雾凝结长大所需的过饱和水汽环境,在测试分析湿法脱硫净烟气中PM_(2.5)及SO_3酸雾物性的基础上,考察了蒸汽及湿空气添加量、脱硫净烟气温度等的影响。结果表明,湿法脱硫净烟气中PM2.5除含有燃煤飞灰外,含Ca SO_4、Ca SO_3及未反应的Ca CO_3等组分;由于SO_3酸雾基本处于亚微米级粒径范围,湿法烟气脱硫(WFGD)系统对SO_3酸雾的脱除率仅为35%-55%;添加适量蒸汽及湿空气方式均可促进湿法脱硫净烟气中PM_(2.5)和SO_3酸雾脱除,最终排放浓度随蒸汽或湿空气添加量的增加而降低,其中,添加蒸汽方式适合于脱硫净烟气温度较低(≤50-55℃)的场合,在脱硫净烟气温度较高(≥55-60℃)时,利用添加湿空气方式替代添加蒸汽更具技术经济优势。     

SO2和NO对ACF低温脱除模拟燃煤烟气中VOC的影响

采用H₂O₂浸渍的方法对活性炭纤维(ACF)进行改性,并利用氮吸附等温线和XPS(X-ray photoelectron spectroscopy)的方法对ACF样品进行表征。通过实验测定改性前后ACF脱除VOC(甲苯作为VOC的代表物)的效果,同时考察二氧化硫(SO₂)和一氧化氮(NO)对ACF脱除甲苯的影响。研究发现,双氧水浸渍改性对ACF的BET表面积和孔容没有影响,但使得ACF样品表面的含氧官能团含量大量增加。实验数据也表明,SO₂和NO对VOC在ACF上的吸附具有抑制作用,且随着两者浓度的增加,抑制作用也增强。 研究还发现,SO₂和NO同时存在比单一的SO₂或NO对VOC在ACF上吸附的抑制作用更为明显。     

臭氧氧化结合湿法喷淋对玻璃窑炉烟气同时脱硫脱硝实验研究

采用臭氧氧化结合湿法喷淋对模拟玻璃窑炉烟气开展了同时脱硫脱硝实验研究.采用不同溶液(NaOH、Na₂S)进行了喷淋实验.结果表明,保证溶液pH值在10以上,NaOH浓度对NO_x脱除效率无影响,SO₂的存在促进了NO_x吸收.当O₃/NO物质的量比为1.6、溶液NaOH浓度为0.5%时,NO_x脱除效率可达70%,SO₂脱除效率在99%以上.往喷淋液中添加Na₂S,NO_x脱除效率随Na₂S浓度增加而提高,SO₂的存在对NO_x脱除效率无影响.当O₃/NO物质的量比为1.2、溶液中NaOH浓度为0.5%、添加剂Na₂S浓度为0.6%时,NO_x脱除效率可达70%,SO₂脱除效率在95%以上.60 min长时间运行实验证明,模拟烟气中的NO_x经碱液和添加剂吸收后主要以NO^-₂的形式存在于喷淋液中,且NO_x脱除效率不随溶液pH值的变化而变化.     

Empirical models for NOx and SO2 removal in a double stage flue gas irradiation process

A multidimensional regression method has been applied to construct empirical model equations of NO_x and SO₂ removal efficiency in e–b process for a two-stage irradiation system based on results achieved for the EPS Kaw czyn pilot plant. The influence of different parameters such as dose, temperature, gas humidity and ammonia stoichiometry have been studied. Model equations describe with satisfactory accuracy experimental results. Therefore obtained models equations can be used for prediction of NO_x and SO₂ removal efficiency in e–b process during two-stage irradiation of flue gases, particularly in the case of scale-up. The results will be implemented in the industrial electron beam flue gas treatment installation being constructed at EPS Pomorzany, Dolna Odra PS Group SA, Poland (flue gas flow 270,000 N m³/h, total beam power of applied accelerators 1.2 MW).     

A shock tube study of vibrational relaxation in SO2, SO2Ar and SO2He

Vibrational relaxation times in SO₂, SO₃Ar (11%, 20% and 54% SO₂) and SO₂He (9.5% SO₂) were measured behind incident shock waves using the laser schlieren technique in the temperature ranges 550–1200 K, 700–2100 K and 700–1600 K respectively for the three systems. An analysis of the density gradient signals revealed a double exponential behaviour consistent with earlier studies. The fast relaxation rates were not quantitatively studied and the slow relaxation rates were found to fit the following equations:

where Pτ is the relaxation time in atm μs and T is in °K. The collision numbers corresponding to the slower rates were found to agree well with a recent theoretical calculation using SSH-Tanczos theory.     

SO2和NO浓度对TiO2-硅酸铝纤维脱除元素汞的影响

使用溶胶凝胶法制备了TiO₂-硅酸铝纤维纳米复合材料。使用此复合材料在波长为253.7 nm的紫外光照射下脱除模拟烟气中的元素汞,实验研究了SO₂和NO浓度对光催化脱汞的影响以及温度对脱汞率的影响。结果表明,常温时烟气中SO₂浓度对光催化脱汞表现出促进作用,当SO₂浓度为1 200 μg/m³时脱汞率最高可达93%。NO浓度对光催化脱汞表现出抑制作用,随着NO浓度的增加脱汞率逐渐降低。高温时SO₂和NO浓度对光催化脱汞的作用规律与常温时相似。随着模拟烟气温度的升高,脱汞率逐渐减低,升高温度对光催化脱汞表现出抑制作用。     

SO2对NO催化氧化过程的影响V.NiO/γ-Al2O3上SO2的作用机理

采用程序升温脱附(TPD)及漫反射原位红外光谱(DRIFT)技术分析比较了SO2存 在前后，NO—02反应气体在NiO／γ—Al2O3催化剂上所形成吸附物种的变化情况， 发现SO2能促使硝酸盐物种在低温分解并释放出NO2，而且耐热稳定的硝酸盐物种也 比单纯NO-02吸附时多．室温时催化剂表面上的SO2以弱吸附物种为主，特征红外吸 收峰位于1324cm^-1附近，温度升高后表面硫酸盐物种数量增多．关联SO2气氛中 NO2的生成规律后得出，类似于铅室反应中间体的多分子吸附物种[NO2(SO3)x]是产 生N02的活性物种，由SO2在载体或催化剂表面弱碱位吸附后吸引气相NO所产生，解 离O^-起到稳定活性物种和补充弱碱位的作用．同时该物种也是毒性物质SO4^2-的 前驱体，当KO氧化反应发生后催化剂的失活也开始了．     

Fast chemisorption of NO and SO2 on FeOOH crystals

The electrical conductivity changes of α-, β- and γ-FeOOH by adsorption of NO and SO₂ during 1 ms-1 min were determined. The conductivity change consists of fast and slow processes which are presumably caused by fast chemisorption on the oxygen vacancies and by slow one on the surface anions. The rate constants of fast and slow chemisorption were determined from the conductivity changes. The correlations of the rate constants with the compression pressure of specimen, adsorption temperature and original electrical conductivity are given. The order of magnitude of the fast chemisorption rate constants of the three polymorphs is related to the difference in the surface structure.     

Bond function parameter transferability in SO2, SF2 and SO2F2

Ab initio MO studies of the use of gaussian bond functions in the molecules SO₂,SF₂ are presented. It is shown that optimization of bond function exponent and position parameters in the small molecules is a good approximation to the optimum parameter set for SO₂F₂,     

蒸汽活化生物质焦吸附模拟烟气中SO2和NO的研究

以麦秆和稻壳生物质为研究对象,在不同的热解温度、热解速率以及蒸汽活化温度条件下制备了生物质焦,采用比表面积与孔隙度分析仪测定生物质焦的比表面积和孔隙结构参数。利用固定床吸附装置,研究了热解温度、热解速率、活化温度和模拟烟气中SO₂和NO浓度等因素对生物质焦吸附SO₂和NO性能的影响。结果表明,蒸汽活化可以显著提高生物质焦的BET比表面积、D-R比表面积、D-R微孔容积和总孔容,降低其平均孔径,并显著增加蒸汽活化生物质焦对SO₂与NO吸附的起始穿透时间和吸附量。快速热解下制得的蒸汽活化焦对SO₂和NO的吸附效果优于慢速热解,热解温度为873 K的蒸汽活化焦的吸附性能明显好于热解温度为673与1 073 K的蒸汽活化焦。在973~1 173 K下,随着蒸汽活化温度的提高,蒸汽活化生物质焦对SO₂和NO的吸附量呈现先上升后下降的趋势。随着模拟烟气中SO₂与NO浓度的降低,蒸汽活化生物质焦对SO₂与NO吸附的起始穿透时间延长,但相应的SO₂和NO吸附量下降。在873 K、快速热解和1 073 K条件下制得的蒸汽活化麦秆焦对SO₂和NO吸附量最大,其值分别为109.02和21.77 mg/g。     

The mechanism of SO2 oxidation by CH3O2 radicals. Rate coefficients for the reactions of CH3O2 with SO2 and NO

The reactions of CH₃O₂ with SO₂ and NO have been studied by steady state photolysis of azomethane in the presence of O₂SO₂→NO mixtures at 296 K and 1 atm total pressure. The quantum yield of NO oxidation by CH₃O₂ radicals is increased substantially when SO₂ is added to the system indicating an SO₂ induced chain oxidation of NO. The rate law gives k₁/k₂ = (2.5 ± 0.5) × 10^?3 for CH₃O₂ + SO₂ → CH₃O₂SO₂ (1), CH₃O₂ + NO → CH₃O + NO₂ (2). Combining this ratio with the absolute value of k₁ = 8.2 × 10^?15 cm³ s^?1 gives k₂ = 10^{?11.5 ± 02} cm³ s^?1.     

ESR study of SO2 on MnO2-alumina

SO ₃ ^– radicals are formed during the reaction between SO₂ and MnO₂-alumina, which suggests that SO ₃ ^– take part in the reduction of Mn⁴⁺ to Mn²⁺.

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SO₂ MnO₂/Al₂O₃ SO ₃ ^– , , SO ₃ ^– Mn⁴⁺ Mn²⁺.

     

Water aerosols spraying for SO2 and NOx removal from gases under E-beam irradiation

The gas-phase transport process of an admixture to the surface of spraying aerosol droplets has been experimentally investigated with reference to E-beam gas cleaning processes. The rate of SO₂ uptake by alkali aerosol droplets with average radius 30 μm has been measured in gas-aerosol jet using light absorption technique. It has been shown that the rate of gas-phase transport is described by the molecular flux of the admixture. Gas-liquid reactions are considered to explain the observed improvement of radiation-induced NO removal in the presence of spraying alkali aerosol.     

CoOx-CeOx/ZrO2催化氧化NO性能及抗SO2毒化研究

采用浸渍法制备了一系列CoO_x-CeO_x/ZrO₂催化剂,探讨了催化剂载体、Co含量、Co/Ce配比等对Co基催化剂催化氧化NO活性的影响及其机理。ZrO₂负载的Co氧化物具有优良的低温NO催化氧化活性,铈的添加进一步提高了催化剂的低温活性。其促进机制主要是提高了催化剂吸附氧的能力及改善了Co在催化剂表面的分散。同时,掺杂铈使得催化剂抗SO₂能力有一定增强,呈现出选择性毒化机制。     

Radiation induced scavenging of NOx, SO2, H2S from exhaust gases

The theoretical model of exhaust gases radiation induced oxidation was developed. NO, SO₂ and H₂S concentrations curves vs dose calculated by use of this model for mixtures containing N₂ (80.5%), O₂ (11%), H₂O (8.4%), NO (100–600 ppm), SO₂ (150–500 ppm) and H₂S (300–1000 ppm) have been obtained. It has been shown that NO and SO₂ conversion reactions with acids formation go simultaneously with oxidizing reaction of H₂S giving SO₂ as an intermediate substance. These processes were evaluated for different initial concentrations of NO, SO₂ and H₂S. Data established by our simulation calculations show that the electron beam process can be judged as a promising technology for simultaneous removal of SO₂, NO and H₂S from exhaust gases.     

High-temperature reduction of SO2 by methane at various CH4/SO2 ratios

The character of the effect of initial reaction mixture and temperature on the selectivity of catalytic reduction of sulfur dioxide by methane in the presence of oxygen has been studied.

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Simultaneous determination of NH3, SO2, NO and NO2 by direct UV-absorption in ambient air

Summary Direct spectroscopic methods are not hampered by wall losses, are highly specific, have a potential for real time detection and offer the possibility to measure several species simultaneously in one experiment. This is demonstrated for the determination of NH₃, NO and SO₂ in ambient air by a differential optical a2bs orption spectroscopy (DOAS) technique in the spectral region 207–221 nm. Detection limits were 1 ng/g or better.     

Calculation of the rate of SO2 oxidation to SO3

Approximate equation to calculate the effectiveness factor of catalyst for SO₂ oxidation to SO₃ has been derived. Calculated data agree well with those predicted by a quasi-homogeneous model.

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