Simultaneous removal of NO/sub x/, SO/sub x/, and CO/sub 2/ at elevated temperature using a plasma-chemical hybrid process

In previous studies, the authors confirmed that the plasma-chemical combined hybrid process for controlling NO flue gas emission was extremely effective and economical in comparison with the conventional selective catalytic reduction (SCR) system and other technologies. In the present study, we carried out experiments on the simultaneous removal of NO/sub x/ and SO/sub x/ at elevated temperature using the plasma-chemical hybrid process. A series of experiments was performed to quantify all the reaction byproducts such as N/sub 2/O, CO, HNO/sub 2/, HNO/sub 3/, NO/sub 3//sup -/, and SO/sub 4//sup -/ to evaluate the simultaneous NO/sub x/ and SO/sub x/ removal efficiency. The oxidation from NO to NO/sub 2/ without decreasing NO/sub x/ concentration (i.e., minimum reaction byproducts) and with least power consumption is the key for the optimum operation of the plasma reactor. The produced NO/sub 2/ was totally converted to N/sub 2/ and Na/sub 2/SO/sub 4/ with Na/sub 2/SO/sub 3/ or Na/sub 2/S with and without NaOH using the barrier-type packed-bed plasma reactor followed by the packed-column chemical reactor. The NO/sub 2/ reduction was more effective for Na/sub 2/S than Na/sub 2/SO/sub 3/ but produces H/sub 2/S with Na/sub 2/S. For both cases at least five times the stoichiometric amount of chemicals were required for complete NO/sub 2/ reduction. Nearly 100% of NO/sub x/ and SO /sub 2/ and 40% Of CO/sub 2/ simultaneous removal were achieved with less than 5 ppm of N/sub 2/O and CO. The operating cost was less than 1/4 the SCR process. The additional SO/sub 2/ treatment system can be eliminated.     

Single-stage plasma-chemical process for particulates, NO/sub x/, and SO/sub x/ simultaneous removal

In a previous study, we investigated the simultaneous removal of NO/sub x/ and SO/sub x/ using a plasma-chemical hybrid process and showed nearly 100% of NO/sub x/ and SO/sub x/ removal. In this study, we investigated simultaneous removal of NO/sub x/, SO/sub x/, and particulates using a single-stage wet-type plasma reactor. This reactor consists of a discharge wire and pyrex cylinder, wrapped by the copper mesh where Na/sub 2/SO/sub 3/ and NaOH solutions flow along the inner wall of the cylinder from the top to the bottom of the reactor. Particulates are charged by pulse corona and collected on the inner wall, and then removed by solutions flow. This method is effective for extremely low. and high-resistivity particles to cause reentrainment or back corona. The plasma was used to oxidize NO to NO/sub 2/, Na/sub 2/SO/sub 3/ solution to reduce NO/sub 2/ to N/sub 2/ and Na/sub 2/SO/sub 4/, and NaOH solution to neutralize nitric and sulfuric acids in the solutions. Without Na/sub 2/SO/sub 3/ and NaOH solutions, 95% of NO removal and no SO/sub 2/ conversion were achieved at 2.5 W. With water, 97% of NO and 64% of NO/sub x/ removal were achieved at 2.6 W, and more than 95% of SO/sub 2/ removal was achieved regardless of the discharge power. With Na/sub 2/SO/sub 3/ and NaOH solutions, 98% of NO and 75% of NO/sub x/ removal were achieved at 2.9 W, and more than 93% of SO/sub 2/ removal was achieved regardless of the discharge power. For the purpose of enhancement of surface reaction on NO/sub 2/ reduction with Na/sub 2/SO/sub 3/, Raschig rings were placed beneath the plasma section with the effective lengths of 5, 10, and 15 cm. As a result, no significant NO/sub x/ removal was obtained in comparison with no Raschig rings. Regarding the removal efficiency of diesel soots using the plasma-chemical hybrid reactor, more than 90% of particulate removal efficiency was obtained.     

PM and $hbox{NO}_{rm x}$ Removal for Diesel Engine Emission Using Ozonizer and Chemical Hybrid Reactor

Over the years, we have investigated particulate matter (PM) and $ hbox{NO}_{rm x}$ reduction using nonthermal plasma-chemical hybrid processes without using catalysts. Among nonthermal plasma hybrid processes, the ozonizer combined with the chemical hybrid reactor was investigated using a 479 cc (5.5 kW) power generation diesel engine. The PM deposited on the diesel particulate filter can be incinerated by ozone and $hbox{NO}_{2}$ in a wide range of flue gas temperature. The NO was oxidized to form $hbox{NO}_{2}$ by ozone, and $hbox{NO}_{2}$ was reduced by the 3% $hbox{Na}_{2}hbox{SO}_{3}$ chemical reactor. As the results, PM deposited on both metal and ceramic filters were successfully removed even at ambient temperature. The rate of PM incineration depends on the amount of ozone injected and was significantly higher than the rate of PM generation. Using 2.4% ozone concentration with a flow rate of 10 L/min, 82% of NO having 720 L/min was oxidized to $hbox{NO}_{2}$, and 78% of $ hbox{NO}_{rm x}$ was removed as a chemical scrubber. However, $ hbox{NO}_{rm x}$ removal was deteriorated about 10% after 1-h operation. This was attributed to $hbox{Na}_{2}hbox{SO}_{3}$ oxidation by air, which was evidenced by the reduction of pH in the chemical reactor.      

气体成分对介质阻挡放电脱除NO影响试验研究

为实现电厂排放达标,通过研究用柱筒型介质阻挡反应器对烟气成分对NO脱除率的影响,主要分析了烟气温度、氧气,二氧化硫和水蒸气含量对脱除率的影响。结果表明:烟气温度对脱除率影响不大。O2的加入使得脱除率降低,氧量越多,脱除率越低。同时NO2的生成量随着含氧量增加而增大。SO2抑制NO的脱除,SO2体积分数越大,脱除率越低。加入水蒸气后,脱除率有明显下降,且水量越高,脱除率越低。水蒸气也会促进NO2的生成。     

SO2与H2 O对商用钒钨钛脱硝催化剂毒化作用综述

选择性催化还原（ＳＣＲ）脱硝技术在火电厂得到广泛应用,烟气组分对催化剂的性能影响及催化剂中毒、细颗粒物产生是当前研究热点。综述重点探讨了工业烟气中SO2、水蒸气（Ｈ２Ｏ）对商用钒钨钛脱硝催化剂的毒化机理、影响因素及控制措施。SO2的毒化机理主要包括硫酸铵盐的覆盖堵塞,催化剂表面活性点位的硫酸盐金属化,以及SO2与NH3、NO的竞争吸附等;H2O的毒化机理主要是其与NH3、NO竞争吸附降低了催化剂的脱硝效率,并促进产生大量的硫酸铵盐,以及阻碍硫酸铵盐与NO的降解反应等。     

Nitric oxide decomposition in air by using nonthermal plasmaprocessing with additives and catalyst

Catalyst (copper-coated zeolite catalyst, i.e., Cu-ZSM-5) was used to enhance NO_x removal plasma chemical reactions. Two kinds of hydrocarbons (2-propane-1-ol, 2-propanol) were added to the synthesized flue gas before the nonthermal plasma process, and their effects on NO_x removal characteristics were investigated. Enhancement effects of NO_x removal by the nonthermal plasma process with hydrocarbons as the additives were confirmed. Usually, the catalyst's working temperature is much higher than the room temperature. A catalytic reactor was installed after the plasma reactor. Catalytic effects on NO_x removal characteristics disappeared when the synthesized flue gas temperature was increased (~250°C). When the synthesized flue gas temperature was at room temperature, about 90% NO _x removal efficiency was realized with a combination of hydrocarbons, the catalytic reactor, and the pulsed discharge plasma     

Hydrogen peroxide and ozone formation in hybrid gas-liquid electrical discharge Reactors

Ozone in the gas phase and hydrogen peroxide in the liquid phase were simultaneously formed in hybrid electrical discharge reactors, known as the hybrid-series and hybrid-parallel reactors, which utilize both gas phase nonthermal plasma formed above the water surface and direct liquid phase corona-like discharge in the water. In the series configuration the high voltage needle-point electrode is submerged and the ground electrode is placed in the gas phase above the water surface. The parallel configuration employs a high voltage electrode in the gas phase and a high voltage needle-point electrode in the liquid phase with the ground electrode placed at the gas-liquid interface. In both hybrid reactors the gas phase concentration of ozone reached a power-dependent steady state, whereas the hybrid-parallel reactor produced a substantially larger amount of ozone than the hybrid series. Hydrogen peroxide was produced in both hybrid reactors at a similar rate to that of a single-phase liquid electrical discharge reactor. The resulting concentration of H/sub 2/O/sub 2/ in the hybrid reactors, however, depended on the pH of the solution and the gas phase ozone concentration since H/sub 2/O/sub 2/ was decomposed by dissolved ozone at high pH.     

Energy Efficiency of Corona Discharge Reactor Driven by Inductive Energy Storage System Pulsed Power Generator

Characteristics of a pulse corona reactor driven by an inductive energy storage (IES) pulsed power generator are described in this paper with focusing on the influence of streamer-to-glow transition on NO removal efficiency. A pulsed high voltage with a short rise time of under 30 ns is employed to generate streamer discharges homogeneously in whole the discharge region. Fast recovery diodes are used as semiconductor opening switch (SOS) to shorten the rise time. The various resistors are employed as dummy load to clarify a suitable circuit parameter such as the capacitance of a primary energy storage capacitor and/or the inductance of a secondary energy storage inductor. The energy transfer efficiency of the pulsed power generator has a maximum value of 50% at 714 Omega dummy load resistance. A co-axial cylinder type discharge chamber was used as the corona discharge plasma reactor driven by the IES pulsed power generator. The pulsed power generator supplies 30 kV pulse with 300 pps repetition rate. The co-axial cylinder plasma reactor consists of 1 mm diameter tungsten wire and 19 mm i.d. copper tube with 30 cm length. NO removal from the simulated diesel engine exhaust gas (N₂:O₂=9:1, Initial NO concentration=200 ppm) increased with input energy into the reactor. The energy efficiency for NO removal was obtained to be 25 g/kWh at 30 % removal in gas flow rate of 2 L/min. However, the energy efficiency decreased to 5 g/kWh with increasing capacitance of the primary capacitor from several hundreds pF to several nF. This decrease was caused by a streamer-to-glow transition. The efficiency was affected by oxygen concentration in the gas mixture.     

Improvement of the energy efficiency in the decomposition of dilute trichloroethylene by the barrier discharge plasma process

In order to improve the energy efficiency in the dilute trichloroethylene (TCE) removal by the nonthermal plasma process, the barrier discharge reactor was studied experimentally. It is investigated by combining it with catalyst of manganese dioxide at the downstream of the barrier discharge reactor. Decomposition efficiency by the barrier discharge reactor was about 83% at the gas flow rate 2 L/min, where the dilute TCE concentration is 250 ppm. Decomposition efficiency with passing through manganese dioxide was improved about 99% at the specific energy of 40 J/L. However, other by-products including ozone and oxidation by-products such as DCAC and TCAA were detected by the gas chromatograph mass spectrometry or the Fourier transform infrared spectroscope measurement. DCAC is generated at the plasma reactor, but TCAA is generated at catalyst during ozone decomposition. CO/sub x/ yield increased about twice with passing through catalyst in the Direct Process. Nitric oxides such as NO, NO/sub 2/, and N/sub 2/O did not generate so much in this barrier discharge process. The dielectric barrier discharge process combined with manganese dioxide is considered as a very desirable way to improve the energy efficiency.     

活性炭纤维负载TiO2同时脱硫脱硝实验研究

为实现烟气同时脱硫脱硝,制备了以活性炭纤维(activated carbon fiber, ACF)为载体,TiO2为光催化剂的复合型光催化剂。在自制的光催化反应器上,用可见光为激发光源,进行了同时脱硫脱硝实验,研究了影响光催化剂同时脱硫脱硝的若干因素。实验结果表明,反应温度、烟气湿度、氧气含量等是影响脱硫脱硝光催化的主要因素,利用扫描电镜(scanning electron microscope, SEM)和X–射线电子能谱(energy spectrometer, EDS)分析了反应前后光催化剂的微观性质,利用离子色谱分析了尾气吸收液的成分,探讨了光催化剂脱硫脱硝的反应机理。在最佳反应温度为100 ℃,烟气湿度为0.006 m3/m3时,SO2和NO的脱除效率分别为97.5%和49.6%。     

Gas cleaning with semi-wet type plasma reactor

An experimental study on the removal of NH₃, NO, NO_x in concentration of 10-40 ppm in air has been carried out using plasma chemical reactions in a streamer corona discharge. The results of the performance of dry type and semi-wet type reactors are compared. The effects of different type of applied voltages such as rectangular pulse, 60-Hz sinusoidal, and 18-kHz alternating voltages are investigated. During NO removal, O₃ and NO₂ are produced. NO₂ can, partially, be removed with higher power input into the discharge. Another undesirable pollutant, namely N₂ O, is also produced, especially, in case of dry reactors having long residence time (~2.4 s). N₂O production decreases, essentially, to zero at 0.6-s residence time while using a semi-wet reactor. In general, higher removal efficiency has been obtained with pulse voltage in a semi-wet reactor. NH₃ in air appears to produce ozone and ammonium nitrate in a discharge. The performance of semi-wet reactors an the removal of submicron dust particles has also been investigated and very high removal efficiency (~93% at 0.6-s residence time) has been obtained     

电晕放电自由基簇射反应器中臭氧的生成

从电极气条件变化着手,对放电过程以及NO脱除过程中自由基簇射反应器内臭氧的生成进行了较为深入的分析。研究结果表明:(1)在相同的放电功率下,当电极气为氧气时产生的臭氧最多,通入空气时其次,而不通电极气时最少;(2)随着电极气湿度的增加,臭氧的产生量逐渐减少;(3)电极气流量的增加提高了臭氧的产生量,但考虑经济性,电极气流量有一最佳值;(4)在NOx脱除过程中,自由基簇射反应器内臭氧浓度大大减少,且随着烟气中NO浓度的增加,臭氧浓度逐渐减少,认为其主要原因是臭氧和氧自由基参与了NO的氧化过程。     

NOx removal by a pipe with nozzle-plate electrode coronadischarge system

The effects of additional gas composition on the corona discharge characteristics in a pipe with nozzle electrode system and the NOx removal characteristics for flue gases are experimentally investigated. The additional gas consists of a mixture of Na+O₂+NH₃ and a small amount of Ar or CO₂, and is introduced to the flue gas stream from the pipe electrode through the corona discharging zone at the tip of nozzles. The results show that corona discharge characteristics and modes are significantly influenced by the composition of the additional gas mixture. Both NO_x reduction rate and energy yield of NO_x removal increase with decreasing corona discharge input power. NO reduction rate and energy yield can be optimized by the type of the additional gas mixture and the flow rates     

NOx removal process using pulsed discharge plasma

Nonequilibrium plasma can be used to promote chemical reactions that reduce the emission of gaseous pollutants, such as NO_x, produced by coal-burning power plants or by diesel engines. Laboratory experiments were carried out to study the decrease of NO_x in simulated flue gases (initial concentration of NO: 200-800 ppm, O₂ : 10%, N₂-balance gas) by means of a pulsed discharge plasma generated in a cylinder type reactor (outer electrode: 20-mm diameter). A rotating spark gap provided square wave high-voltages up to 25-kV, at a frequency of 250 Hz, to corona electrodes of 0.1-, 3.3-, and 6.4-mm diameter. The tests were performed at various temperatures (ambient to 220°C) and constant residence time (0.6 s). The removal performance depended on the size of the discharge electrode and was better at room temperature. The addition of C₂H₄ significantly enhanced the removal performance, concentration of NO_x decreased from 800 ppm to 300 ppm in the discharge. The by-products of this process were analyzed using infrared spectroscopy. No traces of toxic gases could be detected     

Treatment of exhaust gas from vehicles by discharge plasma reactors

The exhaust gas from diesel engines is one of the major causes of air pollution. As one method for pollution control, the authors have been developing plasma reactors. The authors' reactor is a concentric cylinder type which has a glass tube barrier between electrodes. Connecting two of these reactors in series, the NO_x (NO + NO₂) component from diesel engine exhaust gas is decomposed up to 93%. This reactor was mounted on a 3-liter diesel engine and received six-mode load testing at an authorized public facility (JARI, Tsukuba City) and cleared the legal critical value of 350 ppm of NO_x. By this success, the effectiveness of discharge plasma treatment of diesel exhaust gas and its practical evaluation have been confirmed. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 120(2): 1–7, 1997     

应用脉冲放电等离子体氧化NO、SO2的影响因素

在典型的脉冲放电烟气脱硫、脱硝工艺中,NO和SO2主要通过氧化反应转化为相应的高价氨盐化合物脱除,因此如何促进污染物的氧化反应是该技术的关键问题之一。为此,采用丙烯作为添加剂,研究了脉冲频率、烟气中水蒸气的体积分数、注入丙烯的体积分数、SO2等对NO的氧化产物的影响。实验结果表明:烟气中不存在SO2时,NO氧化的主要产物是NO2,且NO2生成的选择性随脉冲频率的上升、水蒸气体积分数的增大而下降,随注入丙烯体积分数的增大而增大。综合考虑到脱硝能耗,丙烯按1倍NOx的体积分数注入烟气为佳;烟气中存在SO2时,NO氧化生成的NO2可以生成硝酸盐,NO2生成的选择性较低,因此SO2可以促进氮氧化物的脱除。     

Regeneration of diesel particulate filter using nonthermal plasma without catalyst

Regulations regarding automotive diesel engine emissions become more severe every year, and it is difficult to meet the requirements with only combustion improvement techniques. More effective post-processing technology is desired especially for particulate matter (PM), such as carbon soots. Although the use of a ceramic diesel particulate filter (DPF) is now a leading technology for PM removal, the problem exists for the soot removal or regeneration at low temperature, especially at cold start. In the present study, a regeneration of a DPF with collected PM was investigated using the low-temperature atmospheric pressure nonthermal plasma. The method is to use the NO/sub 2/ and radicals induced by the plasma reactor to burn carbon soots deposited on the DPF. First, three types of DPF plasma reactors were made and the performance of the conversion of NO to NO/sub 2/ was evaluated at various conditions. Next, a regeneration experiment was carried out using a barrier-type pulse corona plasma reactor. As a result, it was confirmed that the pressure difference decreased when the plasma was turned on and the regeneration of the DPF (approximately 75% of soot removal) was confirmed when the gas temperature was 250/spl deg/C.     

$hbox{NO}_{rm x}$ Aftertreatment Using Thermal Desorption and Nitrogen Nonthermal Plasma Reduction

In this paper, the results of two experiments are reported. First, the performances of various types of nonthermal plasma reactors for $hbox{NO}_{rm x}$ reduction were compared. It was shown that the surface-discharge reactors have as high $ hbox{NO}_{rm x}$ reduction capabilities as pulse-powered wire–cylinder reactors. Second, $hbox{NO}_{rm x}$ treatment using the surface-discharge reactor with a NO-adsorbent zeolite 13X was performed. Thermal desorption was employed for the regeneration of the zeolite. The $hbox{NO}_{rm x}$ of 350 ppm was kept lower than 18 ppm for at least 11 h, whereas it degraded to 75 ppm in the absence of the regeneration. The result suggested the possibility of an aftertreatment system that employed thermal desorption by utilizing the waste heat of diesel engine exhaust and $hbox{NO}_{rm x}$ reduction by using a surface-discharge reactor.      

Industrial experiments on pulse corona simultaneous removal of NOx and SO2 from flue gas

The corona-induced simultaneous removal of NO_x and SO ₂ from flue gas is based on the application of narrow voltage pulses to an electrode structure similar to that of an electrostatic precipitator. The free electrons of the corona discharge, having energy up to 20 eV, originate active radicals which lead to the transformation of NO_x and SO₂ into their acids which can be neutralized to salt particulate by adding to the gas a basic compound such as ammonia and calcium hydroxide. The process has been investigated with a test rig installed in the slipstream of the flue gas duct of a coal-fired thermal power plant. The experiments were performed with three reactor modules of different geometries. Further experiments are necessary to assess the effect of different electrode geometries of the reactor, the efficiency of the process attainable with an improved coupling of narrow pulse power set to the reactor, and the practical ways for integrating the DeNO_x and DeSO₂ corona process with the solid particle collection system     

氨法烟气脱硫过程(NH4)2SO3溶液吸收NOx的特性研究

为研究电厂湿式氨法烟气协同脱硫脱硝过程中的主要吸收剂(NH4)2SO3溶液与烟气中的NOx之间的反应特性,在小型双搅拌反应釜系统中,基于双膜理论对(NH4)2SO3溶液与NOx间的气液吸收反应进行研究.实验结果表明:随气液相搅拌速度和温度的增加,不同NO2/NO之比下的NOx 的吸收速率都相应的增加,而随着O2含量的增加,NO2的吸收速率会不断降低,NO的吸收速率却会不断增加,这主要由于O2的存在涉及到NO和SO32-的同时氧化.另外,由于气相中SO2的存在对NO2和NO的吸收速率都有一定的促进作用,因此氨法同时脱硫脱硝技术具有可行性.