CuO（-CeO2）/SBA-15对萘氧化的催化活性及CO2选择性研究

通过浸渍法制备CuO/SBA-15和CuO-CeO2/SBA-15两种介孔材料催化剂,采用BET、XRD、TPR和XPS等对催化剂进行表征,重点考察催化剂对萘氧化反应的催化活性及对产物CO2的选择性。BET、XRD和XPS等实验结果表明CuO高度分散于介孔分子筛SBA-15中,CeO2可促进CuO在载体上的分散,同时能降低催化剂的TPR还原温度。活性测试结果表明CuO/SBA-15对萘氧化反应的催化活性较高,但是催化氧化的CO2选择性较低,温度在380℃时CO2的生成率仅为60%左右;CeO2的添加不仅提高了CO2的生成率,15%CuO-15%CeO2/SBA-15在325℃使CO2生成率达到99%,而且CeO2增强了催化剂的稳定性。     

CuO-CeO2/AC吸附燃煤烟气中元素汞的实验研究

通过活性炭负载CuO和CeO2来制备吸附剂,采用固定床吸附方式,在不同反应条件下对吸附剂的吸附性能进行测试,筛选出去除效率最好的吸附剂,并通过BET和XRD对吸附剂的理化性质进行分析。结果表明,CuO和CeO2的加入大大改变了原活性炭的比表面积和孔结构,改善了活性炭的吸附性能。CuO-CeO2/AC中CuO和CeO2质量比不同,对汞的去除效率也不同,在1∶2时去除效率最好;CuO-CeO2/AC中所负载的CuO和CeO的总量为5%时,能大大促进汞的吸附效率,增长有效吸附时间;CuO-CeO2/AC对汞的吸附性能随反应温度的增加呈先增加后减小的趋势,在80℃时达到最大值。     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

Effects of acid treatments of activated carbon on its physiochemical structure as a support for copper oxide in DeSO(2) reaction catalysts

To enhance the dispersion of active sites, modification of the AC supports with different acid solution might result in various surface oxygen groups which act as anchoring sites for metallic precursor to stay and improve the reactivity between AC supports and copper precursor. In the present work, the AC support is tailored with HCl and HNO(3), respectively. The pore structure, surface oxygen groups of the AC support and catalysts as well as catalyst dispersion before and after acid treatments are systematically studied by BET, pH(slurry), TPD, and XRPD analyses. It is found that the order of activity in DeSO(2) reaction is as follows: Cu/AC-HCl>Cu/AC>Cu/AC-HNO(3). The same sequence is also observed for the pore structure of AC supports, the catalyst dispersion, but not for the amounts of CO(2) evolving during TPD experiments of supports. The key role of acid treatment on carbon surface chemistry and pore structure, which are closely related to catalyst dispersion and adsorption capacity, is examined to rationalize these findings. Furthermore, under the NO/NH(3)=1 the NO could be selective catalytic reduction with NH(3) in the presence of O(2), which catalyzed by fresh and spent AC-supported catalyst.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

CeO2-CoO／ACF低温SCR烟气脱氮性能的研究

活性炭纤维（ACF）经硝酸处理后采用浸渍法制备了CeO2-CoO／ACF复合催化剂，测试了其在以氨气为还原剂的低温SCR过程中的催化活性，同时研究了金属氧化物浸渍顺序及负载量、催化剂煅烧温度、空速比（SV）、NH，／NO（摩尔比）、O2含量等因素对NO转化效率的影响。研究发现，负载量为10％的CeO2-CoO／ACF复合催化剂经煅烧后在120—240℃时具有很高的催化活性，并且在N0初始浓度为1000mg／m3、空速比（SV）为6000h～、NH3／NO为1．05、O：体积分数在3．0％时具有较高的NO转化效率。     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.     

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Thermodynamic behaviour of sodium and calcium based sorbents in the emission control of waste incinerators

The dry treatment of flue gas produced by incineration processes is discussed thermodynamically. The study investigates the theoretical limits achieved by sodium and calcium based sorbents in the removal of the pollutant species HCl, NOx and SO2. Calculations were performed varying the temperature and the molar ratio between the amount of the injected alkaline sorbent and the content of the pollutant gaseous species in the flue gas. Results show that sodium cation based sorbents are more efficient than calcium based ones in the whole investigated temperature range (100-600 degrees C). The higher effectiveness of sodium based sorbents is particularly remarkable towards hydrogen chloride, whose concentration can always be reduced below the values set by the environmental regulations. Possible improvements in the treatment efficiency of combustion fumes obtainable with sodium based sorbents can be mainly summarised in a lower concentration of HCl in the treated gas and in a partial reduction of NOx concentration.     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

Inorganic PM2.5 at a U.S. agricultural site

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.     

Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.     

CuCoOx／TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx／TiO2催化剂，考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响，并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明，350℃焙烧的催化剂具有CuCo2O4尖晶石结构，比表面积大，对NO的氧化效果好。在空速为5000h^-1，NO进口浓度500mg／m^3，含氧量10％的条件下，反应温度300℃时NO转化率可达79．5％，250℃时NO转化率接近50％。该催化剂具有良好的单独抗SO2、抗H2O毒化性能，H2O和SO2同时存在时很快失活。该催化剂可用于不同时含H2O和SO2的含NO气体催化氧化后再吸收处理。     

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.     

Ti-Ce-Zr-Ox复合脱硝催化剂的制备及其性能研究

采用共混法制备了Ti-Ce-Zr-Ox复合脱硝催化剂TiCe0.1Zr0.1O2.4,运用X射线衍射、氮气物理吸附、扫描电镜等表征手段,分别对该催化剂的晶型、表面积、孔分布及结构形貌进行了分析,同时考察了反应温度、空速、水蒸气和SO2对该催化剂NH3选择性催化还原NO的影响.结果表明,TiCe0.1Zr0.1O2.4催...     

K2Cr2O7溶液同时脱硫脱硝实验研究

采用K2Cr2O7溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,考察多种因素对SO2脱除率(即脱硫率)和NO脱除率(即脱硝率)的影响。实验结果表明:K2Cr2O7浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱硫率、脱硝率影响显著;当烟气流量为0.4L/min,气相中O2体积分数为6%,SO2体积分数为0.09%,NO体积分数为0.100%,K2Cr2O7摩尔浓度为10mmol/L,反应温度为40℃时,脱硫率、脱硝率分别达到100%和64.3%。     

Acidification of a Solonetzic soil by nitrogenous fertilizers

Annual applications of (NH4)2SO4, NH4NO3 and urea on a Solonetzic soil at 112 kg N/ha for 10 consecutive years reduced pH levels from 5.6 for the check to 4.4, 4.9 and 5.3, respectively for (NH4)2SO4, NH4NO3 and urea. (NH4)2SO4 generated twice as much exchange acidity as NH4NO3 and four times as much as urea. Net extractable cations leached from the Ap horizon closely approximated the amount of exchange acidity generated by (NH4)2SO4 and NH4NO3 fertilizers. The levels of soil extractable Al and Mn were greatly enhanced by (NH4)2SO4 as were plant contents. Similar acidifying effects to that produced by the (NH4)2SO4 occurred when NH4NO3 was applied at 300 kg N/ha annually for 12 consecutive years in another field experiment on the same soil. Liming samples of the field (NH4)2SO4 acidified soils in the greenhouse, significantly increased yields and lowered the Al and Mn contents of the plants to normal levels.     

Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.     

Emissions of sulfur trioxide from coal-fired power plants

Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO3 in coal-fired combustion devices such as electric utility boilers. The emissions of SO3 from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO3. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO3 and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.