超重力脱除模拟烟气中一氧化氮简

以NO和N₂的混合气作模拟烟气，以酸性尿素溶液为吸收剂，在超重力机中进行了脱除模拟烟气中NO实验研究。实验考察了混合气中NO初始含量、进气流量、吸收液流量、超重力机转速对NO脱除率的影响，确定了在超重力中尿素吸收NO的适宜条件。实验结果表明，在常温常压下，N₂体积流量为1.0 m³/h，控制NO初始浓度为3 300 mg/m³，吸收液流量为250 L/h，超重力机转速为650 r/min时，NO脱除率可达89.5%。     

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。     

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。     

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。     

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.     

Improved Spray Dry Scrubbing through Grinding of FGD Recycle Material

A laboratory size spray dry scrubbing unit consisting of a spray dryer and a pulse Jet baghouse was used to study the effect of grinding recycle waste on SO₂ removal across the spray dryer and on sorbent utilization. The equipment treats simulated flue gas with a dry flow rate of 1.5 m³ h^?1 (stp) and utilizes an ultrasonic nozzle for atomization. The apparatus was initially tested over a broad range of operating conditions; a close agreement in SO₂ removal was found with data from much larger units. The effect of grinding the FGD recycle material on the SO₂ removal across the spray dryer was found to be great. Grinding the recycle material can enhance the SO₂ removal efficiency to a level comparable to operation with a large excess of fresh lime.     

Application of the Lime/Limestone Flue Gas Desulfurization Process to Smelter Gases

In this presentation, adaptation of the lime/limestone process for flue gas desulfurization (FGD) is discussed and how this process can be adapted to applications in the nonferrous smelting industry such as fugitive gases, copper reverberatory furnace gases, lead sintering gases, molybdenum roasting plant tail gases, and other weak SO₂ smelter gases. Different methods for particulate removal are also discussed with emphasis on how the particulate removal process can be integrated with the desulfurization process.     

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%.     

Laboratory and Field Evaluation of the Controlled Condensation System for S03 Measurements in Flue Gas Streams

The study reported by this paper involves the use of the Controlled Condensation System (Goksoyr/Ross Coil) for flue gas S0₃ measurements in both the laboratory and the field, under low and high mass loadings. The Controlled Condensation System cools the flue gas to below the dewpoint of H₂S0₄ but above the H₂0 dewpoint. The resulting aerosol is collected either on the coil walls or on the back-up glass frit. The laboratory recovery of the H₂S0₄ in streams of varying S0₂, H₂0, and H₂S0₄ content was found to be 95 ± 6%. A new quartz filter holder was designed to meet the filtration problems encountered in collecting S0₃ from particle laden flue gas streams. This quartz system, when heated to above 250°C, quantitatively passed the H₂S0₄ into the condensation coil. Later studies with this filter system preloaded with fly ash equivalent to a mass loading of 1.3 g/m³ yielded a 80-85% recovery of H₂S0₄. The laboratory system was simultaneously tested at a 150 megawatt, pulverized coal-fired power plant prior to and after a wet limestone FGD. The inlet grain loading to the FGD ranged from 0.06 g/m³ to 11.4 g/m³ with S0₂ concentrations as high as 4000 ppm. The average inlet H₂S0₄ value was 8.3 ppm and the outlet from the FGD was 3.1 ppm. The source fluctuation value was determined to be ±65%.     

Technical Description of Parameters Influencing the pH Value of Suspension Absorbent Used in Flue Gas Desulfurization Systems

Abstract

As a result of the large limestone deposits available in Poland, the low cost of reagent acquisition for the large-scale technological use and relatively well-documented processes of flue gas desulfurization (FGD) technologies based on limestone sorbent slurry, wet scrubbing desulfurization is a method of choice in Poland for flue gas treatment in energy production facilities, including power plants and industrial systems. The efficiency of FGD using the above method depends on several technological and kinetic parameters, particularly on the pH value of the sorbent (i.e., ground limestone suspended in water). Consequently, many studies in Poland and abroad address the impact of various parameters on the pH value of the sorbent suspension, such as the average diameter of sorbent particles (related to the limestone pulverization degree), sorbent quality (in terms of pure calcium carbonate [CaCO₃] content of the sorbent material), stoichiometric surfeit of CaCO₃ in relation to sulfur dioxide (SO₂) absorbed from flue gas circulating in the absorption node, time of absorption slurry retention in the absorber tank, chlorine ion concentration in sorbent slurry, and concentration of dissolved metal salts (Na, K, Mg, Fe, Al, and others). This study discusses the results of laboratory-scale tests conducted to establish the effect of the above parameters on the pH value of limestone slurry circulating in the SO₂ absorption node. On the basis of the test results, a correlation equation was postulated to help maintain the desirable pH value at the design phase of the wet FGD process. The postulated equation displays good coincidence between calculated pH values and those obtained using laboratory measurements.     

IV. Recovery of Flue Gas Sulfur as Ammonium Phosphate

The present development in industry has greatly increased the consumption of fossil fuel all over the world. The sulfur present in these fuels on combustion impairs the atmosphere and has to be removed before or after combustion. Direct desulfurization is still in its initial stage of commercial application and is thought to be rather expensive. Most projects today are concerned with flue gas desulfurization and a few people have been successful in the pilot plant scale. Flue gas sulfur is usually recovered as sulfuric acid or ammonium sulfate. The Kiyoura-T.I.T. process employs a completely dry method to recover this sulfur as ammonium sulfate. However, the present trends in fertilizers show that there is a marked drop in the consumption of this type of fertilizer except for China and other Asian countries.

Experiments were carried out to produce a high grade phosphatic fertilizer with a larger field of application. The authors were successful in rendering the phosphate in phosphate rock water soluble by reacting it with the sulfate radical of the ammonium sulfate. Ammonium acid sulfate was used in the experiments and the phosphate radical was determined by a colorimeter utilizing the ammonium molybdate method.

The results showed a conversion and an extractability of 98%, when the molecular ratio of ammonium acid sulfate to the CaO in phosphate rock was in the vicinity of 1:1.4-1.5. The reaction time was 120-180 minutes.

The extracted liquid was crystallized and put through X ray diffractometer experiments which showed that most of the crystals were ammonium phosphate containing about 15% N and 39% P₂O₅ on a dry basis. Thus, it is evident that this could be effectively applied in a commercial scale plant, recovering the flue gas sulfur as ammonium phosphate. The Kiyoura-T.I.T. process can be utilized to recover the flue gas sulfur either as the sulfate or as the phosphate.     

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。     

Thiosulfate as an Oxidation Inhibitor in Flue Gas Desulfurization Processes: A Review of R&D Results

Sodium thiosulfate (Na₂S₂O₃) has been tested in a pilot plant as an oxidation inhibitor in flue gas desulfurization by lime and limestone slurry scrubbing with and without MgO and adiplc acid additives. The effectiveness of thiosulfate is proportional to the inhibitor product, defined as the product of thiosulfate concentration (M), calcium concentration (M), and the moles of SO₂ absorbed per hour per liter of hold tank volume. Gypsum saturation was less than 100 percent and scaling was eliminated when the inhibitor product exceeded 0.3 × 10^?6(gmol/L)³/h. Thiosulfate was relatively more effective in systems with chlorides and less effective in systems promoted by MgO. An inhibitor product greater than 10^?6(gmol/L)³/h significantly enhanced dewatering of solids from limestone scrubbing. SO₂ removal and/or limestone utilization were increased in systems that started with less than 10 mM dissolved calcium.     

Asbestos: Rationale Behind A Proposed Air Quality Standard

A computerized simulation model has been developed to compute energy requirements of a limestone slurry flue gas desulfurization (FGD) system as a function of FGD system design parameters, power plant characteristics, coal properties, and sulfur dioxide emission regulation. Results are illustrated for a "base case" plant of 500 MW, burning 3.5% sulfur coal, meeting the federal new source performance standard of 1.2 lb SO₂/10⁶ Btu. The flue gas is cleaned by an electrostatic precipitator followed by a limestone FGD system with a TCA scrubbing vessel and an optimized in-line steam reheater. The total FGD system energy requirement for this case was found to be 3.4% of the total energy input to the boiler. Sensitivity analyses were then performed in which the nominal values of ten system parameters were individually varied. This caused the total FGD system energy requirement to vary between 2.5 % and 6.1 % of the gross plant output for the range of parameters tested. The most sensitive parameters were found to be scrubbing slurry pH, which affects pumping requirements, and stack gas exit temperature, which affects reheat requirements. In all cases, FGD energy requirements were minimized when the SO₂ emission standard was met by partially bypassing the scrubber. In light of the recent Clean Air Act Amendments this option may not be feasible in the future.     

旋转填料床/柠檬酸盐法吸收-解吸SO2

提出采用旋转填料床结合柠檬酸盐法脱除烟气中SO2的方法,考察了旋转填料床转子转速、液气比、初始柠檬酸根浓度和初始pH值等因素对脱硫效率的影响。结果表明,采用超重力法超重机转子转速为1 000 r/min、液气比为7L/m3、初始柠檬酸根浓度为1.5 mol/L、吸收液的初始pH值为5.0,脱硫效率稳定在99%左右。研究了水蒸气汽提法解吸SO2时初始柠檬酸根浓度、初始pH值、SO2浓度、富液流量和水蒸气流量对解吸效率的影响,得出了影响SO2解吸率的基本规律,并进行了分析。通过实验证明该方法在技术上是可行的,具有良好的应用前景。     

湿式烟气脱硫系统同时脱汞研究

研究表明，湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg²⁺，但对单质汞的吸收效果不明显，因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能，认为在添加剂中，气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好，且不会被SO₂大量消耗，可在WFGD系统实现同时脱硫脱汞；而气态的氯气，液态的K₂S₂O₈溶液虽然也有较好的汞去除效果，但因易被SO₂或亚硫酸盐溶液消耗，当在WFGD系统中用其氧化单质汞时，需要对脱硫塔进行分层或其他改造，使烟气中的SO₂被吸收后再控制汞，提高经济性。     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

Cluster Analysis for Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans Concentrations in Southern Taiwan

Abstract

This study investigates the characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the ambient air of two municipal solid waste incinerators (MSWIs: GS and RW) and a coal-fired power plant (PW) in the Kaohsiung County (KC) area in Taiwan. The results show that the toxic equivalency (TEQ) concentration in the flue gas of GS and RW averaged 0.090 and 0.044 ng international toxic equivalents (I-TEQ)/N·m³, respectively. The TEQ concentration in the flue gas of PW averaged 0.050 ng I-TEQ/N·m³. All PCDD/Fs concentrations from the stack flue gas are lower than the Taiwan Environmental Protection Administration emission standard. Furthermore, the mean I-TEQ concentration in the ambient atmosphere ranged from approximately 0.019 to 0.165 pg I-TEQ/N·m³, much lower than the environmental quality standards for dioxins in Japan (0.6 pg TEQ/N·m³). This work classified all sampling sites into three clusters according to k-means cluster analysis. The result shows a probable direct correlation between the GS incinerator and site C. Although the concentration from the PW plant did not exceed the emission standard, it was much higher than that in Fernández-Martínez’s study. For proper environmental management of dioxins, establishing a complete emission inventory of PCDD/Fs is necessary. The government of Taiwan should particularly pay more attention to power plants to address the information shortage.     

The Effect of Coal Combustion Flue Gas Components on Low-Level Chlorine Speciation Using EPA Method 26A

ABSTRACT

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speci-ating halogen (X₂) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl₂ at high levels (>20 ppm [u,g/m³]) and NH₄Cl in the flue gas stream have been investigated. It has been suggested that precise Cl₂ measurement and accuracy in quantifying HX or X₂ using Method 26A are difficult to achieve at Cl₂ concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl₂ in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl₂ in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speci-ate low levels of Cl₂ accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO₂ is the only component in coal combustion flue gas that has an appreciable effect on Cl₂ distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl₂ in coal combustion flue gas without modification.     

Investigation of aerosol and gas emissions from a coal-fired power plant under various operating conditions

The concentrations of fine particles and selected gas pollutants in the flue gas entering the stack were measured under several common operation modes in an operating coal power plant producing electricity. Particle size distributions in a diameter range from 10 nm to 20 μm were measured by a scanning mobility particle sizer (SMPS), and the flue gas temperature and concentrations of CO₂ and SO₂ were monitored by a continuous emission monitoring system (CEMS). During the test campaign, five plant operating modes were studied: soot blowing, bypass of flue-gas desulfurization (FGD), reheat burner operating at 0% (turned off), 27%, and 42% (normal condition) of its full capacity. For wet and dry aerosols, the measured mode sizes were both around 40 nm, but remarkable differences were observed in the number concentrations (#/cm³, count per square centimeter). A prototype photoionizer enhanced electrostatic precipitator (ESP) showed improved removal efficiency of wet particles at voltages above +11.0 kV. Soot blowing and FGD bypass both increased the total particle number concentration in the flue gas. The temperature was slightly increased by the FGD bypass mode and varied significantly as the rating of reheat burner changed. The variations of CO₂ and SO₂ emissions showed correlations with the trend of total particle number concentration possibly due to the transitions between gas and particle phases. The results are useful in developing coal-fired power plant operation strategies to control fine particle emissions and developing amine-based CO₂ capture technologies without operating and environmental concerns associated with volatile amine emissions.

Implications: The measurement of the fine particle size distributions in the exhaust gas under several common operating conditions of a coal-fired power plant revealed different response relations between aerosol number concentration and the operating condition. A photo-ionizer enhanced ESP was demonstrated to capture fine particles with higher efficiency compared to conventional ESPs, and the removal efficiency increased with the applied voltage. The characteristic information of aerosols and main gaseous pollutants in the exhaust gas is extremely important for developing and deploying CO₂ scrubbers, whose amine emissions and operating effectiveness depends greatly on the upstream concentrations of fine particles, SO₂, from the power plant.