次氯酸钠湿法烟气脱硝及同时脱硫脱硝技术研究

采用NaClO作氧化吸收剂,在鼓泡反应装置进行了湿法烟气脱硝实验研究,考察了NaIO、NO浓度、液相温度、气体流量、pH对脱硝效率的影响以及SO2对同时脱硫脱硝效率的影响,并结合液相产物分析探讨了同时脱硫脱硝反应机理.研究结果表明,pH值是影响活性成分HClO存在形式的重要因素,同时也是影响氧化吸收的关键因素;在一定范...     

Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C3H6

Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.     

介质阻挡放电中添加乙炔对NO脱除的影响

利用介质阻挡放电(DBD)进行模拟烟气脱除NO实验,通过改变乙炔体积分数和烟气水蒸汽含量研究添加乙炔对NO脱除效率的影响.结果表明:烟气中添加乙炔强化了NO氧化作用,随着乙炔体积分数的提高,NO脱除率逐渐增加.在NO/N2/O2/C2H2/H2O体系中,水的电负性和离解反应消耗大量高能电子,降低了活性自由基的生成,NO脱除速率随之减慢;能量密度低于400 J·L-1时,相对湿度(RH)为0的情况下脱出效果最好.但随着能量密度的增加,H2O不会影响最终的NO脱除率;H2O的添加可以产生更多的·OH自由基,促进NO2向HNO3转化,使出口NO2浓度大幅度降低.     

TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal

A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi₅O₇NO₃) surface was synthesized via a precipitation method using TiO₂ and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono-and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi₅O₇NO₃;however, the presence of hydrophilic centres such as TiO₂ and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.     

Effect of TiO2 calcination temperature on the photocatalytic oxidation of gaseous NH3

Carbon-modified titanium dioxide(TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation(PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400℃ had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range( 300℃). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400℃ contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light.     

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density （SED）, and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar 〉 Ar 〉 02/Ar. The highest energy yield of 3.31 g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.     

富氧条件下等离子体协同改性NaY分子筛催化分解NO_x研究

用不同浓度的Cu、Ce和La离子交换Na Y分子筛,对比了不同改性条件下等离子体协同分解NO_x的性能.实验结果表明:Cu是NO_x催化分解的主要活性组分,对于8%Cu-Na Y催化剂,当放电电压为10 k V,放电功率为7.6 W时,NO_x转化率可达46.3%,反应产物中没有NO_2,只有11 ppm的N_2O.Ce的加入可以有效提高催化剂催化活性,对于5%Ce-8%Cu-NaY催化剂,当放电电压为7.8 kV,功率为3.6 W时,NO_x转化率可达67.3%.La的加入同样可以使催化剂活性上升,但不同La含量催化剂的NO_x转化率相差较小.     

Effect of MoO3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.     

TiO2/g-C3N4在泡沫陶瓷表面的负载及光催化空气净化性能增强

以市售P25(TiO_2)和g-C_3N_4为原料,以多孔氧化铝泡沫陶瓷为载体,进行了负载型光催化组件的设计与环境应用.运用浸渍提拉-热处理法制备负载P25/g-C_3N_4的泡沫陶瓷组件,对其微结构进行了表征测试,并将其应用于空气中NO的去除.结果表明,P25/g-C_3N_4在氧化铝泡沫陶瓷表面负载牢固,P25/g-C_3N_4禁带结构匹配有利于光生电荷的分离.研究了P25/g-C_3N_4比例对光催化性能的影响,当g-C_3N_4占P25的量为30%时,负载组件的光催化性能最佳,对NO的去除率达到79.6%.在5次循环反应后,负载型光催化剂表现出良好的稳定性.本研究为P25/g-C_3N_4复合光催化剂的空气净化应用提供了思路和技术基础.     

基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究

富氧燃煤烟气压缩液化CO2的高压低温工况为NO氧化为易溶于水的NO2提供了十分有利的条件.基于小型高压吸收试验装置,采用配制的富氧燃煤模拟烟气,在高压常温下进行了NO、SO2、O2与H2O的吸收反应试验.根据反应前后的气液产物分析,测定了不同组分比例与不同压力下混合气体中NO与SO2的转化率.NO氧化与吸收试验表明,NO转化为HNO3的比率随压力升高而增加,在0.5 ～2 MPa之间增加很快,在2 ～3 MPa之间增速趋丁平缓,压力达3 MPa以上时,90％以上的NO均转化为稀硝酸,且初始NO浓度越高,NO的转化率越大.混合气体中同时存在5O2与NO的联合吸收试验发现,只有少量的NO转化成了NO3-,SO2向H2SO4的转化率随压力升高而增加,初始SO2浓度越大,转化率越高.分析表明,SO2与NO同时存在时SO2先行转化为SO3,NO充当了催化剂,但SO2转化为SO3的一次转化率小于35％,反应酸液产物的多次循环能使SO2的转化率达到90％以上.建议的工艺流程中需采用两座吸收反应塔顺序脱除SO2与NO并回收稀酸溶液,有望在富氧燃煤发电捕集CO2系统中降低脱硫脱硝成本,部分地弥补富氧燃烧机组发电成本的增加.     

可控合成La（OH）3纳米球光催化去除NO及其催化性能机制研究

以KOH和La(NO3)3·6H2O为前驱体,柠檬酸为保护剂,采用一步水热法合成三维La(OH)3纳米球光催化剂.通过XRD、SEM、PL和UV-vis DRS等对样品进行结构表征.结果表明,柠檬酸的加入量对La(OH)3的形貌均匀性和催化活性均有较大影响.柠檬酸和La(NO3)3·6H2O的物质的量的比为2∶1时,得到的样品为形貌均匀的纳米球,光催化活性最佳且稳定性好.这是因为三维的纳米球结构更容易促进光生载流子的分离;此外,形貌均匀无团聚,增加了催化剂表面的活性位点,使反应过程中反应物和中间产物迅速扩散,从而光催化活性最高.在光催化过程中,羟基自由基(·OH)和超氧自由基(·O-2)是最主要的氧化物种.NO可以和产生的·OH和·O-2反应生成HNO2和HNO3,从而去除NO.本文研究结果充实了La(OH)3光催化材料的合成基础理论,探讨了La(OH)3光催化活性机理,为La(OH)3应用打开了新的视野.     

Synergistic effect of F and triggered oxygen vacancies over F-TiO2 on enhancing NO ozonation

Oxidation-absorption technology is a key step for NO_x removal from low-temperature gas. Under the condition of low O₃ concentration (O₃/NO molar ratio = 0.6), F-TiO₂ (F-TiO₂), which is cheap and environmentally friendly, has been prepared as ozonation catalysts for NO oxidation. Catalytic activity tests performed at 120°C showed that the NO oxidation efficiency of F-TiO₂ samples was higher than that of TiO₂ (about 43.7%), and the NO oxidation efficiency of F-TiO₂-0.15 was the highest, which was 65.3%. Combined with physicochemical characteristics of catalysts and the analysis of active species, it was found that there was a synergistic effect between F sites and oxygen vacancies on F-TiO₂, which could accelerate the transformation of monomolecular O₃ into multi-molecule singlet oxygen (¹O₂), thus promoting the selective oxidation of NO to NO₂. The oxidation reaction of NO on F-TiO₂-0.15 follows the Eley-Rideal mechanism, that is, gaseous NO reacts with adsorbed O₃ and finally form NO₂.     

分段进水两级A/O工艺对白酒废水的强化处理效果

为有效控制白酒废水中高质量浓度NH₄+-N对A/O系统冲击引起的出水水质超标问题,分析比较单级A/O工艺和分段进水两级A/O工艺[进水时间（以min计）分配比为7:3]对白酒废水的处理效果.结果表明:与单级A/O工艺相比,分段进水两级A/O工艺出水中ρ（NH₄+-N）、ρ（NO₂--N）、ρ（NO₃--N）和ρ（COD_Cr）均显著降低,其平均去除率分别提高了16.9%、43.2%、49.7%和8%.分段进水两级A/O工艺的二次进水能够为短程硝化反硝化的进行提供有效碳源和NH₄+-N等,为NO₂--N和NO₃--N等去除提供了有利条件;同时,它通过促进对系统内碳源的利用以及NO₂--N的去除,进一步降低了出水中ρ（COD_Cr）.此外,分段进水两级A/O工艺通过降低NH₄+-N和NO₂--N等污染物质量浓度,也能有效减弱其对氨氧化菌和亚硝酸盐氧化菌等微生物的抑制作用,为后续好氧阶段含氮污染物的去除奠定基础.但是,分段进水两级A/O工艺对白酒废水中PO₄3-的去除效果有限,这主要是因为第二阶段的NO₂--N存在使反应系统处于缺氧环境,同时在碳源不充足的情况下,导致聚磷微生物释磷不充分,降低了第二好氧段的吸磷动力.研究显示,分段进水两级A/O工艺能够有效强化白酒废水中三态氮和COD_Cr的降解去除.      

Bi2O3-TiO2复合光催化剂协同处理铬-邻苯二甲酸酯复合污染

以硝酸铋和钛酸丁酯为前驱体,采用水热法制备了Bi_2O_3-TiO_2复合半导体材料,并利用X射线衍射(XRD)、紫外-可见吸收光谱(UVVis)、能谱分析(EDS)、X射线光电子能谱(XPS)等手段对复合材料的结构进行了表征.同时,考察了Bi_2O_3-TiO_2复合材料对重金属Cr(Ⅵ)和难降解邻苯二甲酸二丁酯(DBP)复合污染的处理性能,并探讨了复合催化剂协同处理复合污染的作用机制.结果表明:该复合催化剂在可见光下能同时降低重金属Cr(Ⅵ)和有机物DBP的浓度,抑制电子和空穴复合,表现出比对单一Cr(Ⅵ)及DBP污染物更高的处理效率.当Bi_2O_3含量为4%时,复合催化剂表现出最佳的光催化活性.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

液相氧化-吸收脱除模拟烟气中NOx的研究

分别采用Na Cl O2和Na2SO3溶液作为氧化液和吸收液,在自行设计的鼓泡塔反应系统进行了液相氧化-吸收脱除模拟烟气NOx的研究,考察了气相SO2浓度、Na Cl O2和Na2SO3投加量以及p H值等因素对NO氧化和NOx脱除的影响.结果表明,SO2会优先于NO与氧化剂反应,从而增大氧化剂消耗量.偏酸性条件有利于NO氧化,但酸性太强会导致Na Cl O2分解为Cl O2逸出.碱性吸收液对NO几乎不具吸收脱除效果,但共存NO2能促进NO的吸收脱除.SO2对NO2吸收脱除具有促进作用.     

Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.     

一种新型异养自养集成工艺处理地下水硝酸盐试验

研究了一种利用电化学产氢自养反硝化(electrochemical hydrogen autotrophic denitrification)与固相异养反硝化(solid-phase heterotrophic denitrification)集成技术去除地下水中硝酸盐的方法.这种方法能够高效去除水中的硝酸盐且操作简单.试验结果表明,当进水NO3--N浓度为70mg·mL-1,电流强度控制在40mA,HRT为3.9h时,出水中NO3--N浓度为1.2mg·mL-1,硝态氮去除率达到98.3%,TN去除率达到95.6%,反应器中没有NO2--N积累,且pH值稳定在7.0~8.1之间.     

V2O5/TiO2催化剂中毒机理的试验研究

选择性催化还原(SCR)催化剂是SCR烟气脱硝技术的核心,是整个SCR系统脱硝效率和经济性的决定因素.本文工作的主要研究思路是以钒钛SCR催化剂为研究对象,研究了H2O和SO2,以及相同含量下K、Na、Ca、Pb的氧化物对钒钛催化剂NO转化率的影响.H2O的存在会抑制V2O5/TiO2催化剂脱硝活性,而SO2在一定程度上促进(V2O5/TiO2)催化剂的SCR脱硝反应,提高NO转化率;碱金属K对钒钛催化剂的钝化作用都是最强,K2O和Na2O的掺入会抑制钒钛催化剂上V2O5的还原能力,而CaO和PbO的掺入对钒钛催化剂上V2O5的还原能力影响较小.     

锐钛矿型TiO2光催化降解异噻唑啉酮废水研究

本文制备了自然光照条件下能有效降解异噻唑啉酮模拟废水(主要成分MI和CMI)的锐钛矿型TiO2光催化剂,并通过电镜分析(TEM、HRTEM)和XRD手段对其进行表征,优化了光催化处理异噻唑啉酮模拟废水的反应条件,并分析了异噻唑啉酮的降解产物情况和自然光照条件下羟基自由基的产生情况.结果表明,合成的锐钛矿型TiO2主要暴露面为{101}面,具有较好的异噻唑啉酮去除效果.在500 W氙灯照射下,12~53 mg·L-1异噻唑啉酮模拟废水在催化剂投加量为677 mg·L-1的条件下反应4 h,异噻唑啉酮去除率可以达到97%~100%;当异噻唑啉酮模拟废水浓度升高为141 mg·L-1时,其去除率为77%~80%,最佳反应时间4 h.对异噻唑啉酮降解产物的分析显示,在光催化反应结束时,MI为主要的残留物质,CMI脱氯转化为氯离子和MI,并发现未知有机产物.