CFB烧结烟气脱硫灰亚硫酸钙热氧化条件优化

循环流化床(CFB)是一种常用的半干法烟气脱硫工艺,该工艺的副产物主要为脱硫灰。含有大量亚硫酸钙的脱硫灰较难被利用,致使大量脱硫灰堆积,给环境保护和企业生产带来了巨大的压力。亚硫酸钙的存在限制了脱硫灰在建材领域的应用,只有将其氧化为硫酸钙才能实现其资源化。脱硫灰热氧化主要采用了立式管式炉,分别考察了反应温度、反应状态、氧含量、水汽的含量对亚硫酸钙氧化的影响。结果表明:温度对脱硫灰氧化的影响最大,其次为气体流速、氧含量和水汽含量。反应温度与反应速率呈正相关;增加氧气含量可以提高反应速率,但当氧含量高于30%时,反应速率趋于稳定;反应器温度在350℃时,亚硫酸钙开始缓慢反应,在400℃、无预热气速为75 mL·min~(-1)时,亚硫酸钙最大转化效率达到86%,预热处理后最大转化率达到90%;当水汽量0.88 g·L~(-1)时,水汽量的增加会抑制氧化的进行;当水汽含量0.88 g·L~(-1)时,则会促进反应的进行。以上结果对指导脱硫灰热氧化处理和节能环保具有理论与实践意义。     

硫酸铅在柠檬酸钠-乙酸体系中的浸出转化

硫酸铅可以在柠檬酸钠-乙酸体系中脱硫转化生成柠檬酸铅.考察了柠檬酸钠投加量、反应时间、固液比以及反应温度对PbSO4浸出转化的影响.实验结果表明,PbSO4的转化率随着柠檬酸钠投加量和反应时间的增加而增大,固液比和反应温度对浸出过程影响不大.溶液中溶解的铅含量随着柠檬酸钠投加量的增大而增大,其他条件对其影响不明显.最佳浸出工艺条件是:柠檬酸钠与PbSO4的物质的量之比为2:1,固液比为1/5～ 1/3,反应温度为25℃,反应时间为2h,此时PbSO4的转化率可达到99％左右,溶液中的铅含量为总铅的3.8％左右.PbSO4浸出得到[Pb3(C6H5O7)2]·3H2O,它在350℃左右可完全分解,得到PbO/Pb粉末.     

硫酸铅在柠檬酸钠-酸体系中的浸出转化

硫酸铅可以在柠檬酸钠-乙酸体系中脱硫转化生成柠檬酸铅。考察了柠檬酸钠投加量、反应时间、固液比以及反应温度对PbSO4浸出转化的影响。实验结果表明，PbSO4的转化率随着柠檬酸钠投加量和反应时间的增加而增大，固液比和反应温度对浸出过程影响不大。溶液中溶解的铅含量随着柠檬酸钠投加量的增大而增大，其他条件对其影响不明显。最佳浸出工艺条件是：柠檬酸钠与PbSO。的物质的量之比为2：1，固液比为1／5～1／3，反应温度为25℃，反应时间为2h，此时PbSO4的转化率可达到99％左右，溶液中的铅含量为总铅的3．8％左右。PbSO4浸出得到[Pb，（C。H，O，），]·3H2O，它在350℃左右可完全分解，得到PbO／Pb粉末。     

基于密相半干法脱硫工艺的生石灰消化及改性

以某公司生产的生石灰作为脱硫剂,密相半干法脱硫工艺在某炼铁厂烧结烟气脱硫工程的应用为例,对生石灰的消化反应和调质改性进行实验,考察其满足脱硫要求的最佳消化条件和烧结机头灰作为改性剂的比重。实验表明,当水灰比在1.5～1.7、生石灰粒径在200μm以下、消化温度在55℃左右、搅拌轴转速在15～25 r/min的范围内,可以保证生石灰有最佳的转化率,烧结机头灰占比重的5%时为最佳改性剂量;同时对实验的工程运行成本和脱硫效果进行分析,使用自制改性脱硫剂即可以节约运行成本和水电资源,又能提高脱硫效果,为脱硫设备的长期稳定运行提供了可靠依据。     

烧结烟气脱硫剂性能的研究

为了提高脱硫效率和合理利用烧结过程中产生的机头灰,在半干法烟气脱硫剂生石灰中,加入一定量的烧结机头灰作为脱硫催化剂。在测定机头灰与生石灰化学成分、粒度和比表面积的基础上,研究和分析了机头灰与生石灰的质量配比对于脱硫效率的影响。结果表明,脱硫剂与机头灰在粒径分布和比表面积上都较接近,但经过消化活化后的混合脱硫剂的比表面积明显增大。当机头灰添加量为脱硫剂质量的2%～5%时,脱硫效率提高了2%～3%。机头灰与生石灰的胶凝反应以及机头灰中Fe2O3的催化作用是主要的作用机理。     

脱硫灰中杂质对石灰石脱硫活性的影响

研究脱硫灰中杂质对石灰石脱硫活性的影响具有重要意义,采用烟气湿法脱硫用石灰石粉反应速率的测定方法,使用瑞士万通902智能电位滴定仪,分析了SiO2、Al2O3、Fe2O3、CaSO3与MgO等脱硫灰中5种杂质对石灰石脱硫活性的影响。结果表明,在实验浓度范围内,SiO2、Al2O3、CaSO3的加入在一定程度上促进了石灰石的溶解,而MgO、Fe2O3的加入在一定程度上抑制了石灰石的溶解。将脱硫灰与石灰石掺合作脱硫剂时,要综合考虑这5种杂质对石灰石溶出的影响,选择适宜的脱硫灰和石灰石掺合比。     

氧化锰共生矿烟气脱硫的机理及影响因素

利用南非的氧化锰共生矿进行烟气脱硫,研究了共生锰矿烟气脱硫性能及其机理,并考察了锰矿粒径、反应温度、液固比、进气流量、进口SO_2浓度等因素对脱硫率的影响。结果表明,氧化锰共生矿中主要的锰化合物是MnO_2、Mn_2O_3和MnCO_3,烟气脱硫过程主要存在4种方式:MnO_2与SO_2发生氧化还原反应生成硫酸锰;液相中Mn~(2+)催化氧化SO_2产生硫酸;MnCO_3与硫酸反应生成硫酸锰;Mn_2O_3与硫酸反应后生成的MnO_2可以继续与SO_2进行脱硫反应,但是Mn_2O_3与SO_2直接反应的活性较差。氧化锰共生矿烟气脱硫的最佳工艺参数为:锰矿粒径200目、反应温度80℃、液固比10:1以及进气流量600mL·min~(-1)。     

废铅酸蓄电池铅膏铵法预脱硫过程的动力学分析

以废铅酸蓄电池中铅膏为研究对象,开展了用NH_4HCO_3为脱硫剂对铅膏进行脱硫转化的实验研究。通过分析反应过程中PbSO_4转化率随时间的变化关系,考察了搅拌速度、反应温度及NH_4HCO_3浓度对铅膏脱硫转化的影响;利用固液多相反应的收缩核模型,分析了反应的动力学过程,并计算了反应的表观活化能及表观反应级数。结果表明:在实验选取的条件范围内,提高反应温度、增大NH_4HCO_3浓度及加快搅拌速度均可以促进铅膏的脱硫转化;表观活化能为9.7 kJ·mol~(-1),表观反应级数为0.71,反应过程受内扩散步骤控制。研究结果可为铅膏铵法预脱硫技术能高效、低耗的应用提供参考。     

炼铁烧结除尘灰湿法脱除模拟烟气中的SO2

为了考察炼铁烧结除尘灰作为脱硫剂的效果,研究了湿法脱硫过程中固液比、氧气含量、吸收剂温度、气体流速、进口SO_2质量浓度、搅拌强度等影响因素对脱除效率的影响规律。结果表明,最佳反应温度为25℃;随着温度升高,SO_2溶解度降低,吸收液对SO_2吸收能力降低;气体流量增加,SO_2在吸收剂中停留时间变短,导致脱除率降低;固液比增加,气固接触概率也随之增大,SO_2脱除率也增大;进口SO_2质量浓度的提高导致液相中氢氧根消耗加剧,使反应速率减慢,不利于对SO_2的去除。同时发现,SO_2浓度增加则溶解分数减小,吸收率也会随之降低;搅拌速率的增加使得气泡破碎加剧,增大气液接触面积,使除尘灰充分悬浮在液相中,与溶液中的SO_2迅速反应,有利于SO_2的吸收。O_2含量增加,有利于O_2的溶解,增加了化学反应的推动力,有利于SO_2吸收反应的进行。除尘灰对含二氧化硫气体具有较好的脱硫效果,有一定的应用前景。     

飞灰/水菱镁石新型复合脱硫剂的性能研究

采用飞灰和水菱镁石水合搅拌制备飞灰/水菱镁石新型复合脱硫剂,模拟湿法烟气脱硫过程,采用正交实验分析法探讨了液固比(质量比)、反应温度、搅拌速度以及鼓泡深度4个因素对脱硫效率的影响。结果发现:复合脱硫剂的比表面积增大,这有利于该复合脱硫剂与气相SO2的接触和反应,因而提高了脱硫效率。复合脱硫剂的最佳反应组合:液固比为15.0∶1.0、反应温度为常温(20℃)、搅拌速度为150r/min、鼓泡深度为2.0cm,该条件下脱硫效率为98.58%。     

湿法烟气脱硫反应过程的实验研究

在石灰石/石膏湿法烟气脱硫中试台上,系统开展了浆液pH值、飞灰浓度、液气比、入口SO2浓度、烟气速度和氧化方式等对脱硫反应过程影响的实验研究。实验表明,脱硫效率随着石膏浆液pH值、液气比的升高而增加,且入口SO2浓度越高,液气比越低,影响效应越明显;脱硫效率随着烟气速度、烟气温度和入口SO2浓度的增加而下降;石膏浆液中飞灰含量对系统脱硫效率具有一定的促进作用:pH值>5.6,飞灰浸出液中Fe3+含量相对较低,Fe3+对脱硫反应过渡态催化氧化影响程度较轻,不同工况脱硫效率差别不大。pH值<5.6,飞灰浸出液中Fe3+含量随pH值降低而增大,增效效果逐渐显著;氧化方式对脱硫反应过程有明显的影响,强制氧化工艺的脱硫效率比自然氧化的高5%左右。     

HISTORY of the Air Pollution Control Association

Bottom ash is a waste material from coal-fired power plants, and it is known to contain elements that are potentially toxic at high concentration levels when disposed in landfills. This study investigates the use of bottom ash as a partial substitute sorbent for wet flue gas desulfurization (FGD) processes by focusing on its leaching kinetics in adipic acid. This was studied basing on the shrinking core model that was applied to the experimental data obtained by the authors presented at the International Conference on Industrial, Manufacturing, Automation and Mechanical Engineering, Johannesburg, South Africa, November 27–28, 2013) on dissolution of bottom ash. The leaching rate constant was obtained from different reaction variables, namely, temperature, pH, acid concentration, and solid-to-liquid ratio, that could affect the leaching process. The solid sample of bottom ash was characterized at different leaching periods using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that solid-to-liquid ratio had a significant effect on the leaching rate constant when compared with other variables. The leaching kinetics showed that diffusion through the product layer was the rate-controlling step during leaching, and the activation energy for the process was found to be 18.92 kJ/mol.

Implications:?The use of coal bottom ash waste as a sorbent substitute in wet flue gas desulfurization (FGD) has both economic and environmental advantages. This is because it is a waste from coal-fired thermal power plant and this study has proven that it can leach out a substantial amount of calcium ions for wet FGD process. This will abate anthropogenic pollution due to landfill disposal of bottom ash wastes and also reduce sulfur dioxide emissions.     

Silica-Enhanced Sorbents for Dry Injection Removal of SO2 from Flue Gas

Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO₂ removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO₂ concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)₂ with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO₂ from fly ash and Ca(OH)₂ in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)₂ in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)₂ was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)₂ conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.     

Bench-scale gasification of cedar wood – Part II: Effect of Operational conditions on contaminant release

Here, we present the evolution profile of tar in the product gas during cedar biomass gasification. We also discuss the evolution of other contaminants (H₂S, COS, NH₃, HCN, and HCl). The cedar wood was gasified under various operating conditions in a bench-scale externally heated updraft gasifier; this was followed by thermal reforming.Tar levels in the product gas were significantly affected by the operating conditions used. At a gasification temperature of 923 K, there was no clear relation between the evolution of phenolic tar in the product gas as a function of residence time. The evolution of PAH tar at a low gasification temperature was lower than the evolution of phenolic tar. With increasing temperature, the proportion of PAH tar content became significant. At a gasification temperature of 1223 K, increasing the residence time reduced the content of PAH tar owing to a catalytic effect associated with ash generation at high temperatures. Increasing the steam-to-carbon (S/C) ratio under thermal conditions had a slight effect on PAH conversion. However, increasing the equivalence ratio (ER) effectively reduced the tar levels.The conversion of fuel-sulfur and fuel-nitrogen to volatile-sulfur and volatile-nitrogen, respectively, increased with increasing S/C ratio and ER. The evolutions of COS and HCN gases were much smaller than the evolution of H₂S and NH₃. The evolution of HCl in the product gas decreased slightly with increasing ER. Increasing the S/C ratio decreased the HCl levels in the product gas. The effect of temperature on contaminant levels could not be fully understood due to limited availability of experimental data at various temperatures. We also compare our findings with data in the literature.     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

Current Status of the ADVACATE Process for Flue Gas Desulfurization

The following report discusses current bench- and pilot-plant advances in preparation of ADVAnced siliCATE (ADVACATE) calcium silicate sorbents for flue gas desulfurization. It also discusses current bench- and pilot-plant advances in sorbent preparation. Fly ash was ground in a laboratory scale grinder prior to slurring in order to decrease the slurring time needed for the sorbent to be reactive with SO₂. Reactivity of ADVACATE sorbents with SO₂ in the bench-scale reactor correlated with their surface area.

ADVACATE sorbents produced with ground fly ash were evaluated in the 50 cfm (85 m³/h) pilot plant providing 2 s duct residence time. ADVACATE sorbent was produced by slurrying ground fly ash (median particle size of 4.3 µm) with Ca(OH)₂ at the weight ratio of 3:1 at 90°C (194°F) for 3hto yield solids with 30 weight percent of initial free moisture. When this sorbent was injected into the duct with 1500 ppm SO₂ and at 11°C (20°F) approach to saturation, the measured SO₂ removal was approximately 60percent at a Ca/S stoichiometric ratio of 2. Previously, when ADVACATE sorbent was produced at 90°C (194°F) and at the same fly-ash-to-Ca(OH)₂ weight ratio using unground fly ash, removal under the same conditions in the duct was approximately 50 percent following 12 h slurring. The report presents the results of pilot-scale recycle tests at the recycle ratio of 2. Finally, the report discusses future U.S. Environmental Protection Agency plans for commercialization of ADVACATE.     

From Air Repair to EM: A&WMA’s Publications through a Century of Change

Abstract

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO₂) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO₂ emission is inversely proportional to the parameter y _CO2max, which is equal to the maximum carbon dioxide (CO₂) content by vol ume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

Application of the Active Soda Process for Removing Sulphur Dioxide from Flue Gases

The active soda process1 was applied for desulfurlzatlon of flue gases emitted by a plant burning heavy fuel oil In a rotary drum drier for stone aggregate. The flue gas capacity of the plant was about 6,7 m³/s at normal conditions. The SO₂ concentration varied between 400– 500 ppm. The solid, dry and fine-grained NaHCO₃ of good quality was fed directly into the hot gas stream at the outlet of the rotary drier In two variants—with and without grinding. The mean particle size was 0.180 m^-3 or 0.070 m^-3, respectively. The achieved desulfurizatlon degree was shown to be directly dependent on the flue gas temperature and on the grinding effect, as well as on the normalized stoichiometric ratio. The highest achieved desulfurization degree amounted up to 74 percent. During the design of the desulfurization process no pilot plant installations and tests were necessary, and for the final process no special chemical reactor was used.     

The dissolution kinetics of industrial brine sludge wastes from a chlor-alkali industry as a sorbent for wet flue gas desulfurization (FGD)

The disposal of industrial brine sludge waste (IBSW) in chlor-alkali plants can be avoided by utilization of IBSW as a sorbent in wet flue gas desulfurization (FGD). The shrinking core model was used to determine the dissolution kinetics of IBSW, which is a vital step in wet FGD. The effects of solid-to-liquid ratio (m/v), temperature, pH, particle size, and stirring speed on the conversion and dissolution rate constant are determined. The conversion and dissolution rate constant decreases as the pH, particle size, and solid-to-liquid ratio are increased and increases as the temperature, concentration of acid, and stirring speed are increased. The sorbents before and after dissolution were characterized using x-ray fluorescence (XRF), x-ray diffraction (XRD), and scanning electron microscopy (SEM). An activation energy of 7.195 kJ/mol was obtained and the product layer diffusion model was found to be the rate-controlling step.

Implications: The use of industrial brine sludge waste as an alternative sorbent in wet flue gas desulfurization can reduce the amounts of industrial wastes disposed of in landfills. This study has proved that the sorbent can contain up to 91% calcium carbonate and trace amounts of sulfate, magnesium, and so on. This can be used as new sorbent to reduce the amount of sulfur dioxide in the atmosphere and the by-product gypsum can be used in construction, as a plaster ingredient, as a fertilizer, and for soil conditioning. Therefore, the sorbent has both economic and environmental benefits.