Removal of NOx from Flue Gas with Iron Filings Reduction Following Complex Absorption in Ferrous Chelates Aqueous Solutions

Abstract

A novel process for removal of nitrogen oxides (NO_x) from flue gases with iron filings reduction following complex absorption in iron-ethylenediaminetetraacetic acid aqueous solution is proposed. The reaction mechanism involved in the process is discussed briefly. The parameters influencing the process, including the concentration of ferrous chelates, initial pH, amount of iron filings, temperature, flow rate of the flue gas, and inlet nitric oxide concentration and oxygen content of the flue gas, are researched in detail. The optimal NO_x removal conditions are established. The regeneration and circular utilization of the absorption solution also is studied.     

改性半焦脱除烟气中SO2的研究

对内蒙工业副产褐煤半焦（比表面积49.187m^2／g,孔容0.0351cm^2／g）,采用加压水热化学活化法,HNO3活化法和高温煅烧相结合的方法制备出半焦烟气脱硫剂,并对脱硫剂的脱硫性能进行固定床活性评价。分析表明,其脱硫效果比较好,转化率维持在50％以上的累计硫容可达24．30％,脱硫时间长达35h,远远高于原料半焦的脱硫效果（硫容为0．68％,时间为1．5h）;同时采用水洗法对脱硫剂进行再生,其再生液可用来制备浓度为9.01％的稀硫酸。     

冲天炉烟气除尘净化技术

针对冲天炉熔炼过程中产生污染物的特性，提出了一种净化效率高且经济可行的冲天炉烟气多级复合除尘净化技术。     

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.     

Effect of NOx Control Processes on Mercury Speciation in Utility Flue Gas

Abstract

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NO_x control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NO_x control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH₃, has been evaluated. The influence of NH₃ on fly ash Hg reactions also is being investigated.     

Mechanisms of NOx removal from flue gas by zero valent iron

Chemical reaction between nitric oxide (NO) andzero valent iron (ZVI) was studied in a packed-bed column process with high temperatures based on ZVI strong reducing abilities. For six controlled temperatures of 523-773 K and 400 ppm of NO (typical flue gas temperature and concentration), under short empty bed contacttime ([EBCT] 0.0226-0.0679 sec), NO was completely removed for temperature of 573-773 K but not for 523 K. Break-through curves were conducted for the five working temperatures, and the results indicated that NO reductions by ZVI were varied from 2 to 26.7 mg NO/g ZVI. Higher temperature and longer EBCT achieved better NO removal efficiency. X-ray diffraction (XRD) and electron spectroscopy for chemical analysis (ESCA) were conducted to analyze the crystal structure and oxidation state of the reacted ZVI. Three layers of iron species were detected by XRD: ZVI, Fe3O4, and Fe2O3. ZVI was the most prevalent species, and Fe3O4 and Fe2O3 were less from the XRD analysis. By ESCA, the oxidation state on the reacted ZVI surface was determined, and the species was identifled as Fe2O3, which is the most oxidizing species for iron. Therefore, three layers from the ZVI core to the ZVI surface can be identified: ZVI, Fe3O4, and Fe2O3. Combining the results from XRD and ESCA, the mechanisms for ZVI and NO can be proposed as two consecutive reactions from lower oxidation state (ZVI) in the core to higher oxidation state on the iron surface (Fe2O3): 3Fe + 4NO<--(high temperature)-->Fe3O4 + 2N2 (A1), 4Fe3O4 + 2NO<--(high temperature)-->6Fe2O3 + N2* (A2) Because there was only <5% ZVI used to remove NO comparing to theoretical ZVI used based on the proposed stoichiometry, it can be concluded that the heterogeneous reaction only occurred on the ZVI surface instead of on bulk of the ZVI.     

Plasma versus Thermal Effects in Flue Gas NOx Reduction Using Ammonia Radical Injection

Abstract

A plasma-assisted ammonia injection technique was previously demonstrated as having the potential to remove NO_x from combustion flue gases at SCR-comparable levels without the use of catalysts. However, these demonstrations did not prove the advantage of plasma assistance because they did not explicitly account for enhanced radical production by bulk thermal heating. An experiment using hot ammonia injection was performed to separate this thermal effect from the effect of radical production via interaction with a plasma. Under excess air conditions, results show that a thermal effect does provide improved NO_x reduction, but not to the level achieved with the use of a plasma source. However, heating the injection gases provides only a minor improvement in NO_x reduction at NH₃/NO_x ratios and temperatures typical of commercial cold SNCR applications. The plasma effect in ammonia radical injection was also found to be significant, accounting for an additional 15% to 35% of absolute NO_x reduction beyond any thermal benefit at typical excess air conditions. The ammonia radical injection technique continues to show promise as an effective NO_x reduction alternative.     

Pollutant Removal from Wood and Coal Flue Gases by Soil Treatment

If many homeowners convert to solid fuels for heating, residential flue gases will be a large source of air pollution. Control of this pollution requires an inexpensive, reliable, and effective method of flue gas treatment. One such method is to force flue gases through soil beds. Such soil treatment removes all detectable smoke, odor, and polynuclear organic matter (POM), up to 97% of the CO, and at least 97% of the SO₂ from flue gases of wood and coal combustion. The technique is low cost, reliable, almost maintenance-free, and also appears suitable for other small point sources of air pollution.     

Removal of PCDD/F from Incinerator Flue Gases by Entrained-Phase Adsorption

Abstract

The emission abatement of polychlorinated dioxins and furans (PCDD/F) issued from municipal solid waste incineration is growing in importance because of more stringent emission standards and general concern about their toxic characteristics. These substances cannot be separated by conventional gas cleanup processes but are successfully removed through adsorption onto carbonaceous materials. The simplest technique is the entrained-phase injection of pulverized adsorbents in the flue gas, followed by fabric filter separation. The various related techniques are briefly reviewed here. Operating conditions and results obtained from Flemish MSWIs are given. The results illustrate the excellent overall removal efficiency. Furans are adsorbed to a slightly higher extent than dioxins.

PCDD/F removal by carbonaceous adsorbents is thereafter modeled from first principles for the contribution of both entrained-phase (η₁) and cake filtration (η₂) to the overall efficiency (η_T). Application of the model equations and comparison of measured and predicted overall efficiencies for the Flemish municipal solid waste incinerators (MSWIs) demonstrate that the approach is meaningful and that the dominant parameters are the operating temperature, the dosage and activity of adsorbent, and the fraction of adsorbent in the filter cake. The model equations enable the MSWI operators to predict the adsorption efficiencies for any combination of operating parameters and to assess the sensitivity of the process to varying operating conditions.     

Sulfur Gas Emissions from Flue Gas Desulfurization Sludge Ponds

This paper presents initial measurement data on the emission of volatile, reduced sulfur-containing gases from flue gas desulfurization (FGD) storage ponds. Several different types of FGD stored sludges were studied including lime, limestone, and mixtures of fly ash and lime or limestone residues, some of which had been chemically stabilized. The volatile sulfur gas emissions were cryogenically concentrated and determined by wall-coated, open-tubular capillary column gas chromatography using a flame photometric detector. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and an unusual, unidentified sulfur-containing compound were found in the gaseous pond flux. Benzene, toluene, and α-pinene were also identified by gas chromatography-single ion monitoring mass spectrometry. The total reduced sulfur gas emission from a 100 acre pond approximated 2.0 kg day^?1 (as sulfur).     

TiO2光催化氧化脱除模拟烟气中的NOx

采用P25纳米TiO2为催化剂,对NOx浓度360 mg/m3的模拟烟气进行了光催化氧化实验研究,以期为此种方法在电厂烟气脱硝方面的应用提供依据。经SEM、XRD等表征手段,探讨了催化剂晶型尺寸对光催化的作用。实验考察了光催化反应过程规律以及负载量、光照度、NO初始浓度、O2含量、相对湿度和停留时间对光催化氧化效率的影响。结果表明,光催化反应是瞬态到稳态的过程,其催化效率与上述影响因子有密切关系。实验最优条件下NOx的脱除率为46%,但只需适当提高氧化效能,便能达到理想的效果。     

Resource Recovery from Flue Gas Desulfurization Systems

The cost effective benefits of yielding a flue gas desulfurization (FGD) sludge predominantly composed of CaSO₄·2H₂O, have been previously established. The recovery of this material as FGD by-product gypsum has been demonstrated abroad. Recently U.S. wallboard manufacturers have recognized the viability of this recovery practice. Such techno-economic decision making variables as a) by-product specification, b) transportation costs, and c) location of suitable FGD systems enable the recognition of FGD by-product recovery. Recent investigations of resultant solids content and chloride washing reflect the technical possibility of delivering a suitable product. Commercial and economic factors favor recovery based upon rising disposal and transportation costs. Existing and near term proposed systems surface the technical and commercial problems faced by utilities considering recovery.

Generation of an oxidized FGD sludge consisting of 90⁺% CaSO₄·2H₂O and dewatered to 80⁺% solids is technically achievable by air sparging within the FGD system. Although the product is suitable for land disposal, electric power utilities should consider and evaluate by-product recovery. U.S. wallboard manufacturers have established technical criteria for FGD by-product gypsum. Percent CaSO₄·2H₂O, final solids content, particle size, and chloride content are primarily technical parameters. Technology exists within the FGD industry to satisfy these criteria and results are discussed.

Economic factors comparing mining costs, transportation costs, and disposal costs are developed for specific utility projects. Such comparison established generalized financial criteria for a given utility to develop the economic reasonableness of considering FGD byproduct recovery.

End product user perspectives are presented providing electric utilities with a realistic appreciation for by-product recovery potential. Location of existing wallboard plants highlight potential recovery regions. Quality control problems are discussed in terms of generating a by-product rather than a disposable material.     

不同Cu交换分子筛脱除柴油机尾气中的NOx

以BEA、ZSM-5和SAPO-34分子筛为载体,采用离子交换法制备了用于柴油机尾气中氨选择性催化还原(NH3-SCR)NOx的Cu改性分子筛催化剂.采用XRF、ICP、H2-TPR、和NH3-TPD等表征对催化剂样品的理化特性进行了分析.结果表明,分子筛类型影响铜交换量和铜物种的存在状态.借助H2-TPR和UV-Vis分析可以清晰地看出,在不同类型的分子筛上Cu的还原能力和配位环境明显不同.铜元素引入后,3类分子筛的SCR活性都有明显的改善.3种Cu-交换分子筛的抗高温水热老化能力却明显不同:老化的Cu-SAPO-34依然保持良好脱硝性能而老化的Cu-ZSM-5严重失活.     

亚铁螯合剂液相脱除烟气中NOx

总结了近20多年来液相络合法脱除烟气中NOx的研究成果,详细叙述了亚铁氨羧和亚铁含-SH基二类螯合剂单独脱氮和同时脱硫脱氮的反应机理、动力学、吸收液的再生和过程的影响因素,指出了该工艺存在的主要问题,提出了今后的研究方向.     

硫化碱脱除二氧化硫工业烟气的可行性分析

分析了国内外烟气脱硫的研究现状,论述了用硫化碱脱除二氧化硫化工业烟气在理论上和实验上的可能性。     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

NOx Reduction in a Gas Fired Utility Boiler by Combustion Modifications

Data on the effect of several combustion modifications on the formation of nitrogen oxides and on boiler efficiency were acquired and analyzed for a 110 MW gas fired utility boiler. The results from the study showed that decreasing the oxygen in the flue gas from 2.2% to 0.6% reduced the NO_x formation by 33% and also gave better boiler efficiencies. Flue gas recirculation through the bottom of the firebox was found to be ineffective. Staged combustion was found to reduce the NO_x emissions by as much as 55 % while decreasing the efficiency by about 5%. Adjustment of the burner air registers reduced the NO_x formation by about 20 ppm. The lowest NO_x emissions of 42 ppm (at about 3% O₂) in the stack was obtained for air only to one top burner and 0.5% oxygen in the flue gas.     

Use of Seawater in Flue Gas Desulfurization

For seasite power plants using seawater for condenser cooling, Bechtel developed a new process to remove better than 90 percent of flue gas SO₂ using seawater and lime. Tests demonstrate that marine life is not affected by the effluent from this unique scrubbing process; therefore, the aqueous effluent containing reacted products (gypsum) in solution at low concentration is suitable for discharge to the sea.     

喷射鼓泡法烟气脱硫工艺

对以喷射鼓泡反应器为主设备，石灰石浆液为脱硫剂的湿法烟气脱硫工艺进行了实验研究，结果表明主要参数[烟气压降Δp、ф（液气）比、吸收液pH值、进气SO2浓度]对脱硫效率均有较大的影响。