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.     

Kinetics of selective catalytic reduction of NO by NH_3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH_3.The kinetics of the SCR reaction in the presence of O_2 was studied in this work.The results showed that the observed reaction orders were 0.74-0.99,0.01-0.13,and 0 for NO,O_2 and NH_3 at 350-450℃,respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst.The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N_2 and H_2O.Gaseous O_2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process.It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH_3.     

Effect of oxidation treatment on the adsorption and the stability of mercury on activated carbon

Oxidation treatment on the adsorption and the stability of Hg on activated carbon （AC） was inrestigated. Both MnO2-AC and FeCl3-AC were produced during oxidation treatment. The measurement of modified AC＇s mercury adsorption capacity was conducted in a simulated coal-fired flue gas by adsorbing test apparatus. TCLP and column leaching methods were used to test the stability of mercury adsorbed on ACs. The results indicate that the oxidation treatment changed the pore structure of the AC and modified the carbon surface by creating chemical components such as MnO4^-, Mn^4＋, O, NO^3-, Fe^3＋, Cl^-, etc. The Hg sorption capacity on MnO2-AC or FeCl3-AC was about three times higher than that of untreated carbon. In addition, the mercury control cost of each of the formers was about the half cost of the untreated carbon. The stability of Hg absorption was studied, it found that mercury adsorbed on the oxidation treated AC was not better than that of untreated carbon. It could concluded that the insoluble form of Hg is very important to the stability of mercury adsorbed on AC. This study suggests that the FeCl3-AC is the best absorbent for Hg with high adsorption capacity, better Hg adsorption stability in leaching environment, and lower cost among the three ACs tested.     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

NH3-SCR performance and the resistance to SO2 for Nb doped vanadium based catalyst at low temperatures

Niobium oxide as the promoter was doped in the V/WTi catalyst for the selective catalytic reduction(SCR)of NO.The results showed that the addition of Nb_2O_5could improve the SCR activity at low temperatures and the 6 wt.%additive was an appropriate dosage.The enhanced reaction activity of adsorbed ammonia species and the improved dispersion of vanadium oxide might be the reasons for the elevation of SCR activity at low temperatures.The resistances to SO_2of 3V6Nb/WTi catalyst at different temperatures were investigated.FTIR spectrum and TG-FTIR result indicated that the deposition of ammonium sulfate species was the main deactivation reason at low temperatures,which still exhibited the reactivity with NO above 200°C on the catalyst surface.There was a synergistic effect among NH_3,H_2O and SO_2that NH_3and H_2O both accelerated the catalyst deactivation in the presence of SO_2at 175°C.The thermal treatment at 400°C could regenerate the deactivated catalyst and get SCR activity recovered.The particle and monolith catalysts both kept stable NO_xconversion at 225°C with high concentration of H_2O and SO_2during the long time tests.     

Adsorption performance of CMK-3 and C-FDU-15 in NO removal at low temperature

CMK-3 and C-FDU-15 samples were synthesized using hard-templating and evaporationinduced self-assembly(EISA) methods,respectively.The pore structures of CMK-3 and CFDU-15 as well as commercial activated carbon were characterized by means of X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,and N_2 adsorption–desorption.Adsorption of NO was investigated by means of thermogravimetric analysis,temperature-programmed desorption of NO + O_2,and in situ diffuse reflectance Fourier transform infrared spectroscopy.The results show that the CMK-3 and C-FDU-15 materials possessed ordered and uniform structures.The coadsorption capacity of NO and O_2 decreased in the sequence CMK-3(88.6 mg/g) C-FDU-15(71.7 mg/g) AC(25.3 mg/g).There were two main adsorption species on CMK-3 and CFDU-15:nitrite and nitrate.Nitrite is converted to nitrate easily.However,the adsorption species were more complex on AC,with nitrite being the main species.Moreover,CMK-3 and C-FDU-15 exhibit excellent regeneration efficiency compared with AC.The excellent NO adsorption performance of CMK-3 and C-FDU-15 was associated with their ordered mesoporous structures and high surface areas.The research provides more options for NO adsorption in the future.     

Performance and mechanism study for low-temperature SCR of NO with propylene in excess oxygen over Pt/TiO2 catalyst

A 0.5 wt.% Pt/TiO2 catalyst was prepared and used for the low-temperature selective catalytic reduction(SCR) of NO with C3 H6 in the presence of excess oxygen.The effects of Pt loading and O2 concentration on Pt/TiO2 catalytic performance for low-temperature SCR were investigated.It was found that optimal Pt loading was 0.5 wt.% and excess O2 favored low-temperature SCR of NOx.The mechanism of low-temperature SCR of NO with C3 H6 was investigated with respect to the behavior of adsorbed species over Pt/TiO2 at 150°C using in situ DRIFTS.The results indicated that surface nitrosyl species(Pt δ+-NO and Ti 3+-NO) and Pt 2+-CO are main reaction intermediates during the interactions of NO,C3 H6 and O2.A simplified NO decomposition mechanism for the low-temperature SCR of NO with C3 H6 was proposed.     

Effects of typical algae species (Aphanizomenon flosaquae and Microcystis aeruginosa) on photoreduction of Hg2+ in water body

Photoreduction characteristics of divalent inorganic mercury(Hg~(2+)) in the presence of specific algae species are still not well known. Laboratory experiments were conducted in the present study to identify the effects of different concentrations of living/dead algae species, including Aphanizomenon flosaquae(AF) and Microcystis aeruginosa(MA), on the photoreduction rate of Hg~(2+)under various light conditions. The experimental results showed that percentage reduction of Hg~(2+)was significantly influenced by radiation wavelengths, and dramatically decreased with the presence of algae. The highest percentage reduction of Hg~(2+)was induced by UV-A, followed by UV-B, visible light and dark for both living and dead AF, and the order was dark UV-A UV-B visible light for both living and dead MA. There were two aspects, i.e., energy and attenuation rate of light radiation and excrementitious generated from algae metabolisms, were involved in the processes of Hg~(2+)photoreduction with the presence of algae under different light conditions. The percentage reduction of Hg~(2+)decreased from 15% to 11% when living and dead AF concentrations increased by 10 times(from 106 to 105 cells/mL), and decreased from 11% to ～ 9% in the case of living and dead MA increased. Algae can adsorb Hg~(2+)and decrease the concentration of free Hg~(2+), thus inhibiting Hg~(2+)photoreduction, especially under the conditions with high concentrations of algae. No significant differences were found in percentage reduction of Hg~(2+)between living and dead treatments of algae species.The results are of great importance for understanding the role of algae in Hg~(2+)photoreduction.     

Silver impregnated carbon for adsorption and desorption of elemental mercury vapors

The Hg0 vapor adsorption experimental results on a novel sorbent obtained by impregnating a commercially available activated carbon (Darco G60 from BDH) with silver nitrate were reported. The study was performed by using a fundamental approach, in an apparatus at laboratory scale in which a synthetic flue gas, formed by Hg0 vapors in a nitrogen gas stream, at a given temperature and mercury concentration, was flowed through a fixed bed of adsorbent material. Breakthrough curves and adsorption isotherms were obtained for bed temperatures of 90, 120 and 150°C and for Hg0 concentrations in the gas varying in the range of 0.8–5.0 mg/m3. The experimental gas-solid equilibrium data were used to evaluate the Langmuir parameters and the heat of adsorption. The experimental results showed that silver impregnated carbon was very effective to capture elemental mercury and the amount of mercury adsorbed by the carbon decreased as the bed temperature increased. In addition, to evaluate the possibility of adsorbent recovery, desorption was also studied. Desorption runs showed that both the adsorbing material and the mercury could be easily recovered, since at the end of desorption the residue on solid was almost negligible. The material balance on mercury and the constitutive equations of the adsorption phenomenon were integrated, leading to the evaluation of only one kinetic parameter which fits well both the experimentally determined breakthrough and desorption curves.     

Removal of cyanide adsorbed on pyrite by H2O2 oxidation under alkaline conditions

Large amounts of cyanide tailings are produced during the cyanidation process in gold extraction,which are hazardous solid wastes due to the toxic cyanide.Pyrite is one of the main minerals in cyanide tailings.The removal of cyanide adsorbed on pyrite by H_2O_2 oxidation under alkaline conditions was investigated in this study.It was found that the removal efficiency was positively correlated with pH from 5 to 12,but remained almost constant when pH was higher than 12.The highest cyanide removal efficiency of 91.10% was achieved by adding no less than 0.6 wt.% of H_2O_2.Cyanide removal was positively correlated with the CN~-adsorption amount between 1.06 and 8.5 mg/g,and temperature between 25 and 85°C.The removal of cyanide adsorbed on pyrite by H_2O_2 oxidation under alkaline conditions was due to the oxidation of pyrite.Hexacyanoferrate,thiocyanate and sulfate were generated with mole ratios of about 2.03:1.12:3.17 during the cyanide removal.?2018 The Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences.     

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.     

Treatment of phenol wastewater by microwave-induced CIO_2-CuO_x/Al_2O_3 catalytic oxidation process

The catalyst of CuO_x/Al_2O_3 was prepared by the dipping-sedimentation method usingγ-Al_2O_3 as a supporter.CuO and Cu_2O were loaded on the surface of Al_2O_3,characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).In the presence of CuO_x/Al_2O_3,the microwave-induced chlorine dioxide(ClO_2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol.The factors influencing phenol removal were investigated and the results showed that microwave-induced ClO_2-CuO_x/Al_2O_3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage,extensive pH range.Under a given condition(ClO_2 concentration 80 mg/L,microwave power 50 W,contact time 5 min,catalyst dosage 50 g/L,pH 9),phenol removal percentage approached 92.24%,corresponding to 79.13% of COD_(Cr) removal.The removal of phenol by microwave-induced ClO_2-CuO_x/Al_2O_3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics.Compared with traditional ClO_2 oxidation,ClO_2 catalytic oxidation and microwave-induced ClO_2 oxidation,microwave-induced ClO_2 catalytic oxidation system could significantly enhance the degradation efficiency.It provides an effective technology for the removal of phenol wastewater.     

Effect of competing solutes on arsenic（Ⅴ） adsorption using iron and aluminum oxides

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe_2O_3 and AL_2O_3.The test results indicate that chloride,nitrate and sulfate did not have detectable effects,and that selenium(Ⅳ)(Se(Ⅳ))and vanadium(Ⅴ)(V(Ⅴ)) showed slight effects on the adsorption of As(Ⅴ)with Fe_2O_3.The results also showed that adsorption of As(Ⅴ)on AL_2O_3 was not affected by chloride and nitrate anions,but slightly by Se(Ⅳ)and V(Ⅴ)ions.Unlike the adsorption of As(Ⅴ)with Fe_2O_3,that with Fe_2O_3 was affected by the presence of sulfate in water solutions.Both phosphate and silica have significant adverse effects on the adsorption of As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.Compared to the other tested anions,phosphate anion was found to be the most prominent solute affecting the As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.In general,Fe_2O_3 has a better performance than Al_2O_3 in removal of As(Ⅴ)within a water environment where multi competing solutes are present.     

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.     

VxMn(4 − x)Mo3Ce3/Ti catalysts for selective catalytic reduction of NO by NH3

A series of vanadium based catalysts(VxMn(4-x)Mo3Ce3/Ti) with different vanadium(x wt.%) and manganese((4-x) wt.%) contents have been prepared by the wet impregnation method and investigated for selective catalytic reduction(SCR) of NO_x by NH_3 in the presence of 8 vol.% H_2O and 500 ppm V SO_2.The physicochemical characteristics of the catalysts were thoroughly characterized.The SCR of NO_x by NH_3(NH_3-SCR) activity, especially the low-temperature activity, significantly increased with increasing V_2O_5 content in the catalyst until the V_2O_5 content reached 1.5 wt.%, which corresponds well with the redox properties of the catalyst.All of the metal oxides were well dispersed and strongly interacted with each other on the catalyst surface.V mainly exists in the V~(5+)state in the catalysts.The strong synergistic effect between the vanadium and cerium species led to formation of more Ce~(3+)species, and that between the vanadium and manganese species contributed to formation of more manganese species with low valences.All of the catalysts exhibited strong acidity, while the redox properties determined the NH_3-SCR activity, especially the low-temperature activity.H_2O and SO_2 had severe inhibiting effects on the activity of V1.5Mn2.5Mo3Ce3/Ti.However, good H_2O and SO_2 resistance and high NO_x conversion by V1.5Mn2.5Mo3Ce3/Ti could be achieved in the presence of SO_2 and almost no decline was observed in a long-term test at 275℃ for 168 hr in the presence of SO_2 and H_2O, which can be attributed to the sulfate species formed on the catalyst surface.     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites(Na A, Na X, HZSM-5)impregnated with iron(Ⅲ) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy, and temperature programmed desorption(TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury(Hg0)into oxidized mercury(Hg2+). The crystallization of Na Cl due to the ion exchange effect during the impregnation of Na A and Na X reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of Fe Cl3–HZSM-5 was mainly in the form of mercuric chloride(Hg Cl2), while on Fe Cl3–Na X and Fe Cl3–Na A it was mainly mercuric oxide(Hg O).     

Oxidation inhibition of sulfite in dual alkali FGD system

A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization （FGD） system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and 4）.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed that the consumption rate of thiosulfate agreed well with the laboratory-scale experimental results.