Integrated removal of NO and mercury from coal combustion flue gas using manganese oxides supported on TiO2

A catalyst composed of manganese oxides supported on titania(MnO_x/TiO_2) synthesized by a sol–gel method was selected to remove nitric oxide and mercury jointly at a relatively low temperature in simulated flue gas from coal-fired power plants. The physico-chemical characteristics of catalysts were investigated by X-ray fluorescence(XRF), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS) analyses, etc. The effects of Mn loading,reaction temperature and individual flue gas components on denitration and Hg~0 removal were examined. The results indicated that the optimal Mn/Ti molar ratio was 0.8 and the best working temperature was 240°C for NO conversion. O_2 and a proper ratio of [NH_3]/[NO]are essential for the denitration reaction. Both NO conversion and Hg~0 removal efficiency could reach more than 80% when NO and Hg~0 were removed simultaneously using Mn0.8 Tiat 240°C.Hg~0 removal efficiency slightly declined as the Mn content increased in the catalysts. The reaction temperature had no significant effect on Hg~0 removal efficiency. O_2 and HCl had a promotional effect on Hg~0 removal. SO2 and NH_3were observed to weaken Hg~0 removal because of competitive adsorption. NO first facilitated Hg~0 removal and then had an inhibiting effect as NO concentration increased without O_2, and it exhibited weak inhibition of Hg~0 removal efficiency in the presence of O_2. The oxidation of Hg~0 on Mn O x/TiO_2 follows the Mars–Maessen and Langmuir–Hinshelwood mechanisms.     

Role of NO in Hg oxidation over a commercial selective catalytic reduction catalyst V2O5–WO3/TiO2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V₂O₅–WO₃/TiO₂, to investigate mercury oxidation in the presence of NO and O₂. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O₂. With NO and O₂ pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg⁰ oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O₂. Although NO promoted Hg⁰ oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg⁰ oxidation; NO in the gaseous phase may directly react with the adsorbed Hg⁰, but excessive NO hinders Hg⁰ adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO₂) with oxygen, which facilitated the adsorption and oxidation of Hg⁰. Hg⁰ was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg⁰ temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O₂.     

MoS2 quantum dots based MoS2/HKUST-1 composites for the highly efficient catalytic oxidation of elementary mercury

Due to the ever-tightening regulation on mercury emission in recent decades, there is an urgent need to develop novel materials for the removal of elemental mercury at coal-fired power plants. In this study, a series of MoS₂ quantum dots (QDs)-based MoS₂/HKUST-1 composite materials were prepared. It is found that MoS₂ QDs were encapsulated by HKUST-1 and enhanced the crystallinity and specific surface area of HKUST-1. The MoS₂/HKUST-1 showed excellent performance in catalytic oxidation of Hg⁰ as compared with pristine HKUST-1. It is found that surface layer of lattice oxygens is active and participates in Hg⁰ oxidation, while the consumption of surface oxygens then leads to the formation of oxygen vacancies on the surface. These vacancies are effective in the adsorption and dissociation of O₂, which subsequently participates in the oxidation of Hg⁰. Moreover, the study on the influence of commonly seen gas components, such as SO₂, NO, NH₃ and H₂O, etc., on Hg⁰ oxidation demonstrated that synergistic effects exist among these gas species. It is found that the presence of NO promotes the oxidation of Hg⁰ using oxygen as the oxidant.     

Simultaneous removal of SO2 and NO using a spray dryer absorption (SDA) method combined with O3 oxidation for sintering/pelleting flue gas

Based on the demand of sintering/pelleting flue gas ultra-low emission, a semi-dry method using a spray dryer absorber (SDA) combined with O₃ oxidation was proposed for simultaneous removal of SO₂ and NO. Effects of O₃ injection site, O₃/NO molar ratio, and spray tower temperature on the removal efficiencies were investigated. It was revealed that both desulfurization and denitrification efficiencies could reach to 85% under the conditions of setting O₃ injection site inside of tower, O₃/NO molar ratio 1.8, spray tower temperature 85°C, Ca/(S + 2 N) molar ratio 2.5 and slurry flow rate 300 mL/hr. CaSO₃/Ca(OH)₂ mixture slurry was used as absorbent to simulate operating conditions in iron and steel industry. The result shows that the addition of CaSO₃ weakens both removal efficiencies. In addition, the reaction mechanism of simultaneous removal of SO₂ and NO using SDA combined with O₃ oxidation was proposed.     

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.     

KI改性黏土脱除烟气中单质汞的研究

卤素改性材料对烟气中单质汞的去除具有较高的效率,黏土(膨润土)在我国分布广,资源丰富且廉价易得.为探究KI改性黏土对烟气中单质汞的脱除效率,以浸渍法制得了KI改性膨润土,研究了不同KI负载量、不同吸附温度及不同烟气氛围下,改性膨润土对Hg0的脱除效率和累积吸附量,并与原始膨润土进行对比.运用比表面分析(BET)、傅里叶红外光谱仪(FTIR)及热重分析法(TGA)等方法对材料的物理化学特性进行了分析.结果表明,KI改性大大提升膨润土对Hg0的脱除效率,并且Hg0的脱除效率随着KI负载量的加大而上升.温度提高了吸附剂吸附Hg0的性质,吸附剂主要表现为化学吸附.O2有利于吸附剂对Hg0的吸附.SO2对吸附剂吸附Hg0有轻微的促进作用,H2O的存在对吸附剂吸附Hg0具有很强的抑制作用.     

Absorption characteristics of elemental mercury in mercury chloride solutions

Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.     

Fabrication of Bi2O3/TiO2 nanocomposites and their applications to the degradation of pollutants in air and water under visible-light

A nanoheterojunction composite photocatalyst Bi2O3/TiO2working under visible-light(λ 420 nm) was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.     

Mechanism of Hg oxidation in the presence of HCl over a commercial V2O5–WO3/TiO2 SCR catalyst

Experiments were conducted in a fixed-bed reactor containing a commercial V₂O₅/WO₃/TiO₂ catalyst to investigate mercury oxidation in the presence of HCl and O₂. Mercury oxidation was improved significantly in the presence of HCl and O₂, and the Hg⁰ oxidation efficiencies decreased slowly as the temperature increased from 200 to 400°C. Upon pretreatment with HCl and O₂ at 350°C, the catalyst demonstrated higher catalytic activity for Hg⁰ oxidation. Notably, the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O₂, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg⁰ were first adsorbed onto the catalyst and then reacted with O₂ following its adsorption, which indicates that the oxidation of Hg⁰ over the commercial catalyst followed the Langmuir–Hinshelwood mechanism. Several characterization techniques, including Hg⁰ temperature-programmed desorption (Hg-TPD) and X-ray photoelectron spectroscopy (XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O₂. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

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.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene (HCB) was investigated over several metal oxides (i.e., MgO, CaO, BaO, La₂O₃, CeO₂, MnO₂, Fe₂O₃, and Co₃O₄) supported on Al₂O₃, which was achieved in closed system at a temperature of 300°C. Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents. The decomposition efficiency of different catalysts for this reaction depends on the nature of the metal oxide used, and Al₂O₃ supported La₂O₃ was found to be the most active one. Pentachlorobenzene (PeCB), and all tetrachlorobenzene (TeCB), trichlorobenzene (TrCB), and dichlorobenzene (DCB) isomers were detected after the decomposition reaction, indicating that the decomposition was mainly a dechlorination process. The detection of all lower chlorinated benzenes suggested the complexity of decomposition and the presence of more than one dechlorination pathway.     

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.     

Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO

This study introduced TiO2-pillared clays （TiO2-PILC） as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350℃, the NO conversion was 61% under conditions of GHSV = 23600 hr^-l. The BET data showed that the support particles had a mesoporous structure. Hz-TPR showed that Cr（10）TiP （10 wt.% Cr doping on TiO2-PILC） clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO ＋ O2 adsorption, the intensity of evolution of superoxide ions （O2^-） increased. The content of Cr^3＋ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr^3＋ increased to 50.28%. Additionally, Oα/Oβ increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4^2-.     

Bi2MoO6/Bi2S3异质结光催化降解四环素-铜复合物

利用溶剂热法制备了Bi₂MoO₆/Bi₂S₃异质结材料,采用XRD、TEM、UV-Vis、XPS和光电流响应等表征手段对异质结材料的形貌结构、化学组成和光电性能进行了表征.利用所合成的Bi₂MoO₆/Bi₂S₃对四环素（TC）及四环素-铜（TC-Cu）复合物进行光催化降解.考察了溶液的初始pH,TC初始浓度及TC与Cu²⁺复合量比对TC降解效果的影响.通过自由基捕获实验及中间产物的鉴定探讨了Bi₂MoO₆/Bi₂S₃光催化降解TC和TC-Cu过程的主要活性自由基、中间产物及降解机制;并利用小球藻生长抑制率实验评估了光催化降解过程的毒性.结果表明所制备的Bi₂MoO₆/Bi₂S₃异质结是均匀的纳米片,带隙能为1.76 eV.Bi₂MoO₆与Bi₂S₃质量比为3：1（MS-0.3）异质结对TC浓度为10 mg·L^-1和量比为2：1的TC与Cu²⁺的中性溶液表现出最强的光催化性能,反应60 min后,TC-Cu中TC的去除率和溶液的矿化率分别为85.63%和52.94%.活性基团捕获实验的结果表明,该异质结在可见光下主要的活性物种是·O₂^-.生长抑制率实验结果表明,Cu²⁺的存在降低了复合物中TC光催化降解产物的毒性,光催化氧化可以有效去除复合物中的抗生素.     

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential

Ozone (O₃) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O₃ oxidation. O₃-aged BC particles may change their uptake ability toward trace reducing gases such as SO₂ in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O₃-aged BC and SO₂ was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O₃-aged BC had stronger SO₂ oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO₂. Relative humidity or 254 nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO₂ on O₃-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO₂ reduction, with the consumption of oxidative active sites.     

Ni(NH3)62+ more efficient than Ni(H2O)62+ and Ni(OH)2 for catalyzing water and phenol oxidation on illuminated Bi2MoO6 with visible light

Nickel (hydr)oxide (NiOH) is known to be good co-catalyst for the photoelectrochemical oxidation of water, and for the photocatalytic oxidation of organics on different semiconductors. Herein we report a greatly improved activity of Bi₂MoO₆ (BMO) by nickel hexammine perchlorate (NiNH). Under visible light, phenol oxidation on BMO was slow. After NiNH, NiOH, and Ni²⁺ loading, a maximum rate of phenol oxidation increased by factors of approximately 16, 8.8, and 4.7, respectively. With a BMO electrode, all catalysts inhibited O₂ reduction, enhanced water (photo-)oxidation, and facilitated the charge transfer at solid-liquid interface, respectively, the degree of which was always NiNH > NiOH > Ni²⁺. Solid emission spectra indicated that all catalysts improved the charge separation of BMO, the degree of which also varied as NiNH > NiOH > Ni²⁺. Furthermore, after a phenol-free aqueous suspension of NiNH/BMO was irradiated, there was a considerable Ni(III) species, but a negligible NH₂ radical. Accordingly, a plausible mechanism is proposed, involving the hole oxidation of Ni(II) into Ni(IV), which is reactive to phenol oxidation, and hence promotes O₂ reduction. Because NH₃ is a stronger ligand than H₂O, the Ni(II) oxidation is easier for Ni(NH₃)⁶⁺ than for Ni(H₂O)⁶⁺. This work shows a simple route how to improve BMO photocatalysis through a co-catalyst.     

废茶活性炭脱硫脱硝性能的应用研究

为探讨废茶活性炭对于SO2和NO脱除作用的制约因素,分别考察了材料孔径结构、石墨化程度及表面结构对其脱硫脱硝性能的影响,同时研究了其吸附机制及动力学过程.结果表明,较高的石墨化程度是影响材料脱硫性能的主要因素,微孔径较小且含氮碱性基团较高时有利于SO2的脱除;发达的中孔结构是制约NO脱除效率的关键因素,含氮碱性基团对NO的脱除具有一定的促进作用;烟气中SO2和NO共存时,材料的脱硫脱硝性能均有所降低,氧气和水蒸气的加入能够改善其脱硫脱硝效率;废茶活性炭在无水环境下对于SO2和NO的吸附作用均以物理吸附为主,水蒸气的存在促进了材料对SO2的化学吸附;通过动力学模型的拟合发现,Bangham吸附模型能够很好地描述材料脱硫脱硝的动力学过程,其R2均高于0.989,材料对于SO2和NO的吸附速率常数均随氧气和水蒸气的加入而减小.     

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.