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。     

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。     

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.     

Spray-dry desulfurization of flue gas from heavy oil combustion

An experimental investigation on sulfur dioxide removal in a pilot-scale spray dryer from the flue gas generated by combustion of low-sulfur (S) heavy oil is reported. A limewater slurry was sprayed through an ultrasonic two-fluid atomizer in the spray-dry chamber, and the spent sorbent was collected downstream in a pulse-jet baghouse together with fly ash. Flue gas was sampled at different points to measure the desulfurization efficiency after both the spray-dry chamber and the baghouse. Parametric tests were performed to study the effect of the following variables: gas inlet temperature, difference between gas outlet temperature and adiabatic saturation temperature, lime-to-S ratio, and average size of lime particles in the slurry. Results indicated that spray drying is an effective technology for the desulfurization of low-S fuel oil flue gas, provided operating conditions are chosen carefully. In particular, the lowest gas inlet and outlet temperatures compatible with baghouse operation should be selected, as should a sufficiently high lime-to-S ratio. The attainment of a small lime particle size in the slurry is critical for obtaining a high desulfurization efficiency. A previously presented spray-dry flue gas desulfurization model was used to simulate the pilot-scale desulfurization tests, to check the ability of the model to predict the S capture data and its usefulness as a design tool, minimizing the need for pilot-scale experimentation. Comparison between model and experimental results was fairly good for the whole range of calcium/S ratios considered.     

Electric Utility Applications Of Fabric Filters

Encouraged by the successes attained with fly ash control by fabric filters in Pennsylvania Power & Light and Colorado Ute, other utilities are installing, planning, and/or considering baghouses as a practical and economical means for controlling emissions from the burning of low sulfur coals. Where deposits of alkaline reagents (i.e. nahcolite) are available, some power plants are also considering a process for dry scrubbing SO₂ from the flue gas. By introducing such reagents with the emission ahead of the fabric collector, both partlculates and SO₂ are removed.     

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.     

Carbon dioxide capture strategies from flue gas using microalgae: a review

Global warming and pollution are the twin crises experienced globally. Biological offset of these crises are gaining importance because of its zero waste production and the ability of the organisms to thrive under extreme or polluted condition. In this context, this review highlights the recent developments in carbon dioxide (CO₂) capture from flue gas using microalgae and finding the best microalgal remediation strategy through contrast and comparison of different strategies. Different flue gas microalgal remediation strategies discussed are as follows: (i) Flue gas to CO₂ gas segregation using adsorbents for microalgal mitigation, (ii) CO₂ separation from flue gas using absorbents and later regeneration for microalgal mitigation, (iii) Flue gas to liquid conversion for direct microalgal mitigation, and (iv) direct flue gas mitigation using microalgae. This work also studies the economic feasibility of microalgal production. The study discloses that the direct convening of flue gas with high carbon dioxide content, into microalgal system is cost-effective.     

Environmental Irradiation Test Facility

Results from a detailed analysis of sulfur dioxide (SO₂) reductions achievable through “deep” physical coal cleaning (PCC) at 20 coal-fired power plants in the Ohio-Indiana-Illinois region are presented here. These plants all have capacities larger than 500 MWe, are currently without any flue gas desulfurization (FGD) systems, and burn coal of greater than l%sulfur content (in 1980). Their aggregate emissions of 2.4 million tons of SO₂ per year represents 55% of the SO₂ inventory for these states. The principal coal supplies for each power plant were identified and characterized as to coal seam and county of origin, so that published coal-washability data could be matched to each supplier. The SO₂ reductions that would result from deep cleaning each coal (Level 4) were calculated using an Argonne computer model that assumes a weight recovery of 80%. Percentage reductions in sulfur content ranged from zero to 52%, with a mean value of 29%, and costs ranged from a low of $364/ton SO₂ removed to over $2000/ton SO₂ removed. Because coal suppliers to these power plants employ some voluntary coal cleaning, the anticipated emissions reduction from current levels should be near 20%. Costs then were estimated for FGD systems designed to remove the same amount of SO₂ as was achieved by PCC through the use of partial scrubbing with bypass of the remaining flue gas. On this basis, PCC was more cost-effective than FGD for about 50% of the plants studied and had comparable costs for another 25% of the plants. Possible governmental actions to either encourage or mandate coal cleaning were identified and evaluated     

用于气态零价汞转化的催化剂研究

零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。     

Gas Cleaning Systems for the High Temperature,High Pressure Fluidized Bed Coal Combustor

The high temperature, high pressure fluidized bed coal combustor concept is intended to deliver a low dust content combustion gas at 1600°F and 11 atmospheres to a gas turbine for electricity generation. The perceived advantages of the system are 1) 15-20% increase in fuel efficiency and 2) flue gas desulfurization by adding crushed limestone to the fluidized bed combustor. A major R & D effort, supported by DOE, EPA, EPRI, and others, was undertaken to identify one or more gas cleaning systems of commercial size capable of 1) meeting EPA’s new source performance standards for coal burning power plants and 2) operating reliably under the severe environmental conditions specified. The principal gas cleaning systems that have been investigated for this service include: ceramic cleanable cloth filters, granular bed filters, rigid, porous ceramic structures, and electrostatic precipitators. Some of the fly ash collectors have been operated up to pilot scale size under realistic conditions. In spite of several years of intensive effort and many millions of dollars expended, production of a commercial unit has not been realized. A major content of this paper is a review of the accomplishments and failures of each of the fly ash collector concepts and a series of recommendations to guide future R & D efforts.     

半干法烟气脱硫除尘多级功能处理装置技术与应用

文中介绍了一种炉窑烟气调质、烟气除尘、烟气脱硫在一个单体结构中的一体化装置和在烟气除尘脱硫技术上的应用,并对该脱硫除尘装置与传统的半干法烟气脱硫除尘装置进行了比较。     

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.     

Development of a 24-Hour Method for Analysis of SO2 and CO2 from Electric Utility Units Equipped with Flue Gas Desulfurization Scrubbers

A procedure was developed for the 24-h determination of SO₂ and CO₂ in effluent gas from fossil fuel combustion sources. Laboratory experiments were conducted to test absorption of SO₂ in hydrogen peroxide solution and absorption of CO₂ by sodium hydroxide on an inert substrate at expected ambient temperatures of 15 to 45°C. Isopropyl alcohol cannot be used to trap sulfuric acid and particulates because it permeates the sampling train and prevents complete absorption of CO₂. Elemental analysis of stack particulates revealed that at least 31 elements were present. Iron and other elements interfered with SO₂ analysis. These particulates were completely removed by a heated borosilicate glass filter. Both laboratory and field experiments showed that molecular sieves are a promising alternative for CO₂ absorption. Statistical evaluation of data collected at three units equipped with flue gas desulfurization scrubbers proved that the new procedure is accurate and precise.     

基于响应曲面法优化烧结烟气脱硫灰改性工艺

采用BOX-Behnken的中心组合实验设计及响应面分析方法对半干法烧结烟气脱硫灰进行改性研究,得到脱硫灰转化率的预测模型。结果表明:通过该预测模型可以很好地描述脱硫灰的转化率与反应温度、反应时间和气固比等重要操作参数之间的关系,R2=0.9903。因素分析表明,反应温度对脱硫灰的转化率影响最大,同时反应温度和气固比的交互作用与反应温度和时间的交互作用对脱硫灰的转化率的影响作用相同。利用得到的改进预测模型可以计算脱硫灰的转化率。     

A New Catalytic Reactor for Nitrogen Oxides Removal

The body of information presented in this paper is directed to those individuals concerned with the catalytic NO_x removal reactor for a dirty (containing dust) flue gas. In the case of treating a dirty flue gas, the concentration of dust is the most important factor. While the dirty gas passes through the catalytic reactor, dust particles deposit and plug up the catalyst causing the reactor pressure loss to rise. As a result, the NO_x reduction efficiency decreases more and more, and continuous operation becomes impossible. A new type of NO_x removal reactor for dirty flue gas, the intermittent moving bed reactor, has been developed. The following characteristics have been evaluated: (1) method of calculating reactor pressure loss caused by dust particles, (2) static pressure distribution across the catalyst bed in the reactor, (3) method of evaluating uniform movement of catalyst and (4) reentrainment pattern of dust by catalyst movement. After carrying out various successful pilot plant tests, the information needed for construction and operation of a commercial plant has been developed.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

氢氧化钠-钢渣双碱法烧结烟气脱硫工艺

在鼓泡反应器中考察了氢氧化钠-钢渣双碱法烧结烟气脱硫的主要影响因素。结果表明,在温度为常温,钢渣反应时间为2 h,钢渣加入量为40 g,SO2进口浓度为2 400 mg/m3,钢渣粒径为200目以上,烟气流量为0.05 m3/h,循环液pH保持在7～8,Na+浓度为0.5 mol/L,循环液为500 mL的条件下,脱硫率可长时间保持在80%以上。同时,对钢渣-氢氧化钠双碱法烧结烟气脱硫机理进行了探讨。     

Development and Pilot Plant Evaluation of Silica- Enhanced Lime Sorbents for Dry Flue Gas Desulfurization

EPA’s efforts to develop low cost, retrofitable flue gas cleaning technology include the development of highly reactive sorbents. Recent work addressing lime enhancement and testing at the bench-scale followed by evaluation of the more promising sorbents in a pilot plant are discussed here.

The conversion of Ca(OH)₂ with SO₂ increased several-fold compared with Ca(OH)₂ alone when Ca(OH)₂ was slurrled with fly ash first and later exposed to SO₂ in a laboratory packed bed reactor. Ca(OH)₂ enhancement increased with the increased fly ash amount. Dlatomaceous earths were very effective reactivity promoters of lime-based sorbents. Differential scanning calorimetry of the promoted sorbents revealed the formation of a new phase (calcium silicate hydrates) after hydration, which may be the basis for the observed Improved SO₂ capture.

Fly ash/lime and diatomaceous earth/lime sorbents were tested in a 100 m³/h pilot facility incorporating a gas humidifier, a sorbent duct injection system, and a baghouse. The inlet SO₂ concentration range was 1000-2500 ppm. With once-through dry sorbent injection into the humidified flue gas [approach to saturation 10–20°C (18–36°F) in the baghouse], the total SO₂ removal ranged from 50 to 90 percent for a stoichiometric ratio of 1 to 2. Recycling the collected solids resulted in a total lime utilization exceeding 80–90 percent. Increased lime utilization was also investigated by the use of additives.     

The Fate and Behavior of Mercury in Coal-Fired Power Plants

Abstract

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 ± 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 ± 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%.

On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only ~3 μg/m_STP ³ at 6% O₂. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing.

Speciation of Hg is a very important factor. An oxidized form (HgCl₂) favors a high degree of removal. The conversion from Hg⁰ to HgCl₂ is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.     

Comparison of particle emissions from small heavy fuel oil and wood-fired boilers

Flue gas emissions of wood and heavy fuel oil (HFO) fired district heating units of size range 4–15 MW were studied. The emission measurements included analyses of particle mass, number and size distributions, particle chemical compositions and gaseous emissions. Thermodynamic equilibrium calculations were carried out to interpret the experimental findings.In wood combustion, PM1 (fine particle emission) was mainly formed of K, S and Cl, released from the fuel. In addition PM1 contained small amounts of organic material, CO₃, Na and different metals of which Zn was the most abundant. The fine particles from HFO combustion contained varying transient metals and Na that originate from the fuel, sulphuric acid, elemental carbon (soot) and organic material. The majority of particles were formed at high temperature (>800 °C) from V, Ni, Fe and Na. At the flue gas dew point (125 °C in undiluted flue gas) sulphuric acid condensed forming a liquid layer on the particles. This increases the PM1 substantially and may lead to partial dissolution of the metallic cores.Wood-fired grate boilers had 6–21-fold PM1 and 2–23-fold total suspended particle (TSP) concentrations upstream of the particle filters when compared to those of HFO-fired boilers. However, the use of single field electrostatic precipitators (ESP) in wood-fired grate boilers decreased particle emissions to same level or even lower as in HFO combustion. On the other hand, particles released from the HFO boilers were clearly smaller and higher in number concentration than those of wood boilers with ESPs. In addition, in contrast to wood combustion, HFO boilers produce notable SO₂ emissions that contribute to secondary particle formation in the atmosphere. Due to vast differences in concentrations of gaseous and particle emissions and in the physical and chemical properties of the particles, HFO and wood fuel based energy production units are likely to have very different effects on health and climate.