Supercritical water oxidation of sulfide

Supercritical water oxidation (SCWO) of sulfide wastewater with oxygen as the oxidant was investigated using ammonium sulfide solution as the model waste. The experiments, which were conducted in a bench-scale continuous SCWO installation, indicated that S2- could be completely oxidized to SO4(2-) within the residence time of less than 10 s under the supercritical water conditions at 698.2-773.2 K and 22.0 MPa-30.0 MPa. The reaction pathway of S2- in SCWO was determined to be S2- --> S2O3(2-) --> SO3(2-) --> SO4(2-). The effects of temperature, pressure, and oxygen content on SCWO of S2- were also studied. The kinetic model based on this pathway was established with the reaction rate constants and orders found by fitting the experimental data. The dependence of the rate constants on the temperature can be described with Arrhenius' law. The rate constants are dependent on the density of SCW, and the dependence is logarithmically linear.     

Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8-12.6 and 15-45 degrees C

The oxidation rate of arsenopyrite by dissolved oxygen was measured using a mixed flow reactor at dissolved O2 concentrations of 0.007-0.77 mM, pH 1.8-12.6, and temperatures of 15-45 degrees C. As(III) was the dominant redox species (>75%) in the experimental system, and the As(III)/As(V) ratio of effluent waters did not change with pH. The results were used to derive the following rate law expression (valid between pH 1.8 and 6.4): r = 10((-2211 +/- 57)T) (mO2)(0.45 +/- 0.05), where r is the rate of release of dissolved As in mol m(-2) s(-1) and T is in Kelvin. Activation energies (Ea) for oxidation of arsenopyrite by 02 at pH 1.8 and 5.9 are 43 and 57 kJ/mol, respectively, and they compare to an Ea value of 16 kJ/mol for oxidation by Fe(III) at pH 1.8. Apparent As release rates passed through a minimum in the pH range 7-8, which may have been due to oxidation of Fe2+ to hydrous ferric oxide (HFO) with attenuation of dissolved As onto the freshly precipitated HFO.     

Degradation of dicarboxylic acids (C2-C9) upon liquid-phase reactions with O3 and its atmospheric implications

Aerosols are considered major players in climate change and represent health hazards. Dicarboxylic acids are among a major class of components that form secondary organic atmospheric aerosols. To understand the atmospheric transformation of these compounds, kinetic studies on the ozonolysis and the photoinduced ozonolysis (lambda > or = 250 nm) of aqueous solutions of seven (C2-C9) dicarboxylic acids, which have been identified in atmospheric aerosols, were performed using Fourier transform infrared and ultraviolet-visible spectroscopy. The measured apparent rate constants for dicarboxylic acids in 0.1 mol L(-1) aqueous solutions at 298 +/- 2 K are as follows: oxalic, (2.7 +/- 0.1) x 10(-2); malonic, (5.5 +/- 0.1); succinic, (6.7 +/- 0.4) x 10(-4); glutaric, (1.3 +/- 0.2) x 10(-3); adipic, (1.7 +/- 0.1) x 10(-3); pimelic, (4.4 +/- 0.1) x 10(-3); and pinic, (2.5 +/- 0.1) x 10(-2) (L mol(-1) s(-1)). An empirical equation is provided to estimate the ozonolysis rate constant of dicarboxylic acids containing more than three carbon atoms for which no experimental data exists. A mechanism for malonic acid ozonolysis, which explains its fast ozonolysis rate constant, is also suggested. The implications of our results to atmospheric chemistry indicate that ozonolysis and photoinduced ozonolysis are not significant removal pathways for dicarboxylic acids.     

Rate coefficients for the OH + pinonaldehyde (C10H16O2) reaction between 297 and 374 K

The rate coefficientforthe reaction of OH with pinonaldehyde (C10H16O2, 3-acetyl-2,2-dimethyl-cyclobutyl-ethanal), a product of the atmospheric oxidation of alpha-pinene, was measured under pseudo-first-order conditions in OH at temperatures between 297 and 374 K at 55 and 96 Torr (He). Laser induced fluorescence (LIF) was used to monitor OH in the presence of pinonaldehyde following its production by 248 nm pulsed laser photolysis of H2O2. The reaction exhibits a negative temperature dependence with an Arrhenius expression of k1(T) = (4.5 +/- 1.3) x 10(-12) exp((600 +/- 100)/ 7) cm3 molecule(-1) s(-1); k1(297 K) = (3.46 +/- 0.4) x 10(-11) cm3 molecule(-1) s(-1). There was no observed dependence of the rate coefficient on pressure. Our results are compared with previous relative rate determinations of k1 near 297 K and the discrepancies are discussed. The state of knowledge for the atmospheric processing of pinonaldehyde is reviewed, and its role as a marker for alpha-pinene (monoterpene) chemistry in the atmosphere is discussed.     

Impact of humidity on the ozone initiated oxidation of limonene, delta3-carene, and alpha-pinene

The effect of water on the initial secondary organic aerosol (SOA) formation from gas-phase ozonolysis of limonene, delta3-carene, and alpha-pinene (-3 and approximately 1.5 x 10(11) molecule cm(-3) reacted) has been investigated in a flow reactor at controlled relative humidity (RH), temperature (298 +/- 0.4 K), and reaction time (270 +/- 2 s). Low amounts of terpene converted minimize the impact of secondary reactions. A comparison of the SOA formation from the three terpenes was made for initial rate of reactions being around 7.5 x 10(8) and 15 x 10(8) molecule cm(-3) s(-1). The most efficient species in producing SOA was limonene, while alpha-pinene was the least efficient. The results showed that an enhancement in water vapor concentration (<2-85% RH) caused an increase in both integrated mass (M10-300nm) and total number (N10-300nm). The effect on number and mass were a factor of 2-3 and 4-8, respectively. Physical water up-take can partly explain the increase in mass, but not the observed increase in number. Therefore it was concluded that the increase in water concentration must, by a gas-phase reaction, produce more low volatility product(s).     

Development of regenerable MgO-based sorbent promoted with K2CO3 for CO2 capture at low temperatures

To improve their CO2 absorption capacity, alkali-based sorbents prepared by impregnation and wet mixing method of potassium carbonate on supports such as activated carbon and MgO (KACI30, KACP30, KMgI30, and KMgP30), were investigated in a fixed bed reactor (C02 absorption at 50-100 degrees C and regeneration at 150-400 degrees C). Total CO2 capture capacities of KMgI30-500 and KMgP30-500 were 178.6 and 197.6 mg CO2/g sorbent, respectively, in the presence of 11 vol % H2O even at 50 degrees C. The large amount of CO2 capture capacity of KMgP30-500 and KMgI30-500 could be explained by the fact that MgO itself, as well as K2CO3, could absorb CO2 in the presence of water vapor even at low temperatures. In particular, water vapor plays an important role in the CO2 absorption of MgO and KMgI30-500 even at low temperatures below 60 degrees C, in marked contrast to MgO and CaO which can absorb CO2 at high temperatures. The CO2 capture capacity of the KMgI30-300 sorbent, however, was less than that of KMgI30-500 due to the formation of Mg(OH)2 which did not absorb CO2. MgO based-sorbents promoted with K2CO3 after CO2 absorption formed new structures such as K2Mg(CO3)2 and K2Mg(CO3)2 x 4(H2O), unlike KACI30 which showed only the KHCO3 crystal structure. The new Mg-based sorbents promoted with K2CO3 showed excellent characteristics in that it could satisfy a large amount of CO2 absorption at low temperatures, a high CO2 absorption rate, and fast and complete regeneration.     

Atmospheric chemistry of 2-ethoxy-3,3,4,4,5-pentafluorotetrahydro-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-furan: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of the title compound which we refer to as RfOC2H5. Rate constants of k(Cl + RfOC2H5) = (2.70 +/- 0.36) x 10(-12), k(OH + RfOC2H5) = (5.93 +/- 0.85) x 10(-14), and k(Cl + RfOCHO) = (1.34 +/- 0.20) x 10(-14) cm3 molecule(-1') s(-1) were measured in 700 Torr of N2, or air, diluent at 294 +/- 1 K. From the value of k(OH + RfOC2H5) the atmospheric lifetime of RfOC2H5 was estimated to be 1 year. Two competing loss mechanisms for RfOCH(O*)CH3 radicals were identified in 700 Torr of N2/O2 diluent at 294 +/- 1 K; decomposition via C-C bond scission giving a formate (RfOCHO), or reaction with 02 giving an acetate (RfOC(O)CH3). In 700 Torr of N2/O2 diluent at 294 +/- 1 K the rate constant ratio k(O2)/k(diss) = (1.26 +/- 0.74) x 10(-19) cm3 molecule(-1). The OH radical initiated atmospheric oxidation of RfOC2H5 gives Rf0CHO and RfOC(O)CH3 as major products. RfOC2H5 has a global warming potential of approximately 55 for a 100 year horizon. The results are discussed with respect to the atmospheric chemistry and environmental impact of RfOC2H5.     

Selective oxidation of key functional groups in cyanotoxins during drinking water ozonation

Chemical kinetics were determined for the reactions of ozone and hydroxyl radicals with the three cyanotoxins microcystin-LR (MC-LR), cylindrospermopsin (CYN) and anatoxin-a (ANTX). The second-order rate constants (k(O3)) at pH 8 were 4.1 +/- 0.1 x 10(5) M(-1) s(-1) for MC-LR, approximately 3.4 x 10(5) M(-1) s(-1) for CYN, and approximately 6.4 x 10(4) M(-1) s(-1) for ANTX. The reaction of ozone with MC-LR exhibits a k(O3) similar to that of the conjugated diene in sorbic acid (9.6 +/- 0.3 x 10(5) M(-1) s(-1)) at pH 8. The pH dependence and value of k(O3) for CYN at pH > 8 (approximately 2.5 +/- 0.1 x 10(6) M(-1) s(-1)) are similar to deprotonated amines of 6-methyluracil. The k(O3) of ANTX at pH > 9 (approximately 8.7 +/- 2.2 x 10(5) M(-1) s(-1)) agrees with that of neutral diethylamine, and the value at pH < 8 (2.8 +/- 0.2 x 10(4) M(-1) s(-1)) corresponds to an olefin. Second-order rate constants for reaction with OH radicals (*OH), k(OH) for cyanotoxins were measured at pH 7 to be 1.1 +/- 0.01 x 10(10) M(-1) s(-1) for MC-LR, 5.5 +/- 0.01 x 10(9) M(-1) s(-1) for CYN, and 3.0 +/- 0.02 x 10(9) M(-1) s(-1) for ANTX. Natural waters from Switzerland and Finland were examined for the influence of variations of dissolved organic matter, SUVA254, and alkalinity on cyanotoxin oxidation. For a Swiss water (1.6 mg/L DOC), 0.2, 0.4, and 0.8 mg/L ozone doses were required for 95% oxidation of MC-LR, CYN, and ANTX, respectively. For the Finnish water (13.1 mg/L DOC), >2 mg/L ozone dose was required for each toxin. The contribution of hydroxyl radicals to toxin oxidation during ozonation of natural water was greatest for ANTX > CYN > MC-LR. Overall, the order of reactivity of cyanotoxins during ozonation of natural waters corresponds to the relative magnitudes of the second-order rate constants for their reaction with ozone and *OH. Ozone primarily attacks the structural moieties responsible for the toxic effects of MC-LR, CYN, and ANTX, suggesting that ozone selectively detoxifies these cyanotoxins.     

超临界水氧化法处理黑液

造纸黑液是一种相当难处理的高浓度工业废水,本文以工业纯氧为氧化剂,用自制的间歇式超临界水氧化系统处理造纸黑液,实验结果表明:选定最佳的实验参数后,超临界水氧化法可使黑液中COD和色度的去除率分别达到99.9%和99.5%。     

Formation quotients of aluminum sulfate complexes in NaCF3SO3 media at 10, 25, and 50 degrees C from potentiometric titrations using a mercury/mercurous sulfate electrode concentration cell

Mercury/mercurous sulfate electrode concentration cells (with liquid junction) are employed in this study to determine the formation constants of aluminum sulfate complexes, with the principal advantage that the change in the free sulfate concentration is measured directly without the need to know the standard potential of the electrode. Potentiometric titrations were conducted at temperatures of 10, 25, and 50 degrees C and ionic strengths of approximately 0.3, 0.5, and 1.0 molal in aqueous solutions of the inert 1:1 electrolyte sodium trifluoromethanesulfonate (NaTr). Stoichiometric molal formation quotients Q1 and Q2, respectively, for the reactions Al3+(aq) + SO4(2-)(aq) AlSO4+(aq) and Al3+(aq) + 2SO4(2-)(aq) <= >Al(SO4)2-(aq) were determined. The values of log Q1 obtained from this work in NaTr media at ionic strengths of 0.3 and 1.0 mol x kg(-1) and 50 degrees C (1.72 +/- 0.08 and 1.35 +/- 0.06, respectively) are in excellent agreement with the values (1.71 +/- 0.2 and 1.32 +/- 0.1) determined in NaCl media from the recent potentiometric study conducted in the same laboratory using a hydrogen electrode concentration cell by Ridley et al. (Ridley, M. K.; Wesolowski, D. J.; Palmer, D. A.; Kettler, R. M. Geochim. Cosmochim. Acta 1999, 62, 459-472). The value of log Q2 (2.05 +/- 0.05) in 1.0 mol x kg(-1) from this work is smaller than the value reported by Ridley et al. (2.6 +/- 0.5) but within the combined experimental error. Empirical isothermal equations are presented to permit calculation of the equilibrium quotients as a function of ionic strength (0-1 mol x kg(-1)), giving log K1 and log K2 values at 25 degrees C and infinite dilution of 3.84 +/- 0.12 and 5.58 + 0.09, respectively. The value for log K1 obtained in this study at 25 degrees C is bracketed within experimental uncertainty by values reported by Kryzhanovskii et al. (Kryzhanovskii, M. M.; Volokhov, Y. A.; Pavlov, L. N.; Eremin, N. I.; Mironov, V. E Zh. Prikl. Khim. 1971, 44,476-479) and Nishide and Tsuchiya (Nishide, T.; Tsuchiya, R. Bull. Chem. Soc. Jpn. 1965, 38, 1398-1400), namely, 3.89 and 3.73, respectively. All other literature values for the first aluminum sulfate association constant are considerably lower than these results, which is also true for the second association constant, although there are few experimental data available for the latter. Empirical equations are also presented for calculating values of log Q1 and log Q2 from 0 to 1 molal ionic strength and from 10 to 125 degrees C, spanning the range of most environmental conditions at which these reactions are important.     

Atmospheric chemistry of HFE-7500 [n-C3F7CF(OC2H5)CF(CF3)2]: reaction with OH radicals and Cl atoms and atmospheric fate of n-C3F7CF(OCHO*)CF(CF3)2 and n-C3F7CF(OCH2CH2O*)CF(CF3)2 radicals

Relative rate techniques were used to measure k(OH + HFE-7500) = (2.6+/-0.6) x 10(-14), k(Cl + HFE-7500) = (2.3+/-0.7) x 10(-12), k[Cl + n-C3F7CF(OC(O)H)CF(CF3)2] = (9.7+/-1.4) x 10(-15), and k[Cl + n-C3F7CF(OC(O)CH3)CF(CF3)2] < 6 x 10(-17) cm3 molecule(-1) s(-1) at 295 K [HFE-7500 = n-C3F7-CF(OC2H5)CF(CF3)2]. From the value of k(OH + HFE-7500) an estimate of 2.2 years for the atmospheric lifetime of HFE-7500 is obtained. Two competing loss mechanisms for n-C3F7-CF(OCHO.CH3)CF(CF3)2 radicals were identified in 700 Torr of N2/O2 diluent at 295 K; reaction with O2 and decomposition via C-C bond scission with kO2/k(decomp) = 0.013+/-0.006 Torr(-1). The Cl atom initiated oxidation of HFE-7500 in N2/O2 diluent gives n-C3F7CF(OC(O)CH3)CF(CF3)2 as the major product and n-C3F7CF(OC(O)H)CF(CF3)2 as a minor product. The atmospheric oxidation of HFE-7500 gives n-C3F7-CF(OC(O)CH3)CF(CF3)2 and n-C3F7CF(OC(O)H)CF(CF3)2 as oxidation products. The results are discussed with respect to the atmospheric chemistry and environmental impact of HFE-7500.     

Hydrogen generation in microbial reverse-electrodialysis electrolysis cells using a heat-regenerated salt solution

Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m(3) H(2)/m(3)·d, with a hydrogen yield of 3.4 mol H(2)/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes.     

The OH-initiated oxidation of hexylene glycol and diacetone alcohol

The OH-initiated oxidation of two VOCs directly emitted to the atmosphere through their use as industrial solvents, hexylene glycol (HG, (CH3)2C(OH)CH2CH(OH)CH3) and diacetone alcohol (DA, (CH3)2C(OH)CH2C(O)CH3), has been studied in two photoreactors: a 140 L Teflon bag irradiated by lamps at CNRS-Orleans and the 200 m3 European photoreactor, EUPHORE, irradiated by sunlight. The rate constants for the reactions of HG and DA with OH radicals have been determined at (298 +/- 3) K using a relative rate method: k(HG) = (1.5 +/- 0.4) x 10(-11) and k(DA) = (3.6 +/- 0.6) x 10(-12) cm(3) molecule(-1) s(-1) and have been found in good agreement with estimations from structure-reactivity relationships. The study at Orleans and EUPHORE of the OH-initiated oxidation of hexylene glycol showed the formation of diacetone alcohol, acetone, and PAN as the principal products. The branching ratio of the H-atom abstraction from the > CH- group of HG has been estimated to be (47 +/- 4)% corresponding to the measured formation yield of DA. The formation yields of acetone and PAN lead to the determination of a lower limit of (33 +/- 7)% for the branching ratio of the H-atom abstraction of the -CH2- group of HG. For diacetone alcohol, studies at EUPHORE have shown negligible photolysis under atmospheric conditions (J < 5 x 10(-6) s(-1)) and the formation of acetone, PAN, HCHO, and CO in the OH-initiated oxidation experiments. The molar yield of acetone, close to 100%, corresponds to the branching ratio of the H-atom abstraction from the -CH2- group of DA. The present study has allowed the identification of the nature and the fate of the oxy radicals as intermediates in the oxidation mechanism of both HG and DA. The atmospheric implication of these results, especially the ozone formation potential of HG and DA, is discussed.     

Oxidation of chlorinated ethenes by heat-activated persulfate: kinetics and products

In situ chemical oxidation (ISCO) and in situ thermal remediation (ISTR) are applicable to treatment of groundwater contaminated with chlorinated ethenes. ISCO with persulfate (S2O8(2-)) requires activation, and this can be achieved with the heat from ISTR, so there may be advantages to combining these technologies. To explore this possibility, we determined the kinetics and products of chlorinated ethene oxidation with heat-activated persulfate and compared them to the temperature dependence of other degradation pathways. The kinetics of chlorinated ethene disappearance were pseudo-first-order for 1-2 half-lives, and the resulting rate constants-measured from 30 to 70 degrees C--fit the Arrhenius equation, yielding apparent activation energies of 101 +/- 4 kJ mol(-1) for tetrachloroethene (PCE), 108 +/- 3 kJ mol(-1) for trichloroethene (TCE), 144 +/- 5 kJ mol(-1) for cis-1,2-dichloroethene (cis-DCE), and 141 +/- 2 kJ mol(-1) for trans-1,2-dichloroethene (trans-DCE). Chlorinated byproducts were observed, but most of the parent material was completely dechlorinated. Arrhenius parameters for hydrolysis and oxidation by persulfate or permanganate were used to calculate rates of chlorinated ethene degradation by these processes over the range of temperatures relevant to ISTR and the range of oxidant concentrations and pH relevant to ISCO.     

Operation of a two-stage fermentation process producing hydrogen and methane from organic waste

A pilot-scale experimental plant for the production of hydrogen and methane by a two-stage fermentation process was constructed and operated using a mixture of pulverized garbage and shredded paper wastes. Thermophilic hydrogen fermentation was established at 60 degrees C in the first bioreactor by inoculating with seed microflora. Following the hydrogenogenic process, methanogenesis in the second bioreactor was conducted at 55 degrees C using an internal recirculation packed-bed reactor (IRPR). After conducting steady-state operations under a few selected conditions, the overall hydraulic retention time was optimized at 8 d (hydrogenogenesis, 1.2 d; methanogenesis, 6.8 d), producing 5.4 m3/m3/d of hydrogen and 6.1 m3/m3/d of methane with chemical oxygen demand and volatile suspended solid removal efficiencies of 79.3% and 87.8%, respectively. Maximum hydrogen production yield was calculated to be 2.4 mol/mol hexose and 56 L/kg COD loaded. The methanogenic performance of the IRPR was stable, although the organic loading rate and the composition of the effluent from the hydrogenogenic process fluctuated substantially. A clone library analysis of the microflora in the hydrogenogenic reactor indicated that hydrogen-producing Thermoanaerobacterium-related organisms in the inoculum were active in the hydrogen fermentation of garbage and paper wastes, although no aseptic operations were applied. We speculate that the operation at high temperature and the inoculation of thermophiles enabled the selective growth of the introduced microorganisms and gave hydrogen fermentation efficiencies comparable to laboratory experiments. This is the first report on fermentative production of hydrogen and methane from organic waste at an actual level.     

Methanol oxidation using ozone on titania-supported vanadia catalyst

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100-250 degrees C using a V2O5/ TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. The oxidation of methanol with ozone in the absence of a catalyst gave about 30% conversion at 100 degrees C. Methanol oxidation over a V2O5/TiO2 catalyst at 100 degrees C gave very little conversion with oxygen, whereas the conversion increased to 80% with ozone. Methanol, having an inlet stream concentration of 15 000 ppmv, can be completely oxidized to CO(x) with an ozone-to-methanol ratio of 1.2, a temperature of 150 degrees C, and a gas hourly space velocity (GHSV) of 60 000 h(-1). The apparent activation energy with ozone was calculated to be ca. 40 kJ/mol, which is much lower than that calculated with oxygen (60 kJ/mol). At low methanol conversion methyl formate was the main product, whereas higher conversions favored oxidation to CO(x). The results imply a consecutive reaction of adsorbed methanol species, favoring selectivity toward methyl formate at lower temperatures and ozone-to-methanol ratios and CO(x) at higher temperatures and ozone-to-methanol ratios. Langmuir-Hinshelwood kinetics was used to model the reaction with and without ozone in the feed. The model parameters were obtained using least-squares fit to a selected set of experimental data, and the model was subsequently compared to all experimental data obtained in this study.     

Atmospheric HFEs degradation in the gas phase: reactions of HFE-7100 and HFE-7200 with Cl atoms at low temperatures

Kinetic rate coefficients for the reactions of HFE-7100 (1) (C4F9OCH3) and HFE-7200 (2) (C4F9OC2H5) with Cl atoms have been measured using a discharge flow mass spectrometric technique (DFMS) at 1 Torr total pressure. The reactions have been studied under pseudo-first-order kinetic conditions in excess of HFEs over Cl atoms and the study has been extended from 333 down to 234 K to approach the tropospheric temperature profile. At room temperature the measured rate constants are k (1) = (1.43 +/- 0.28) x 10(-13) cm3molecule(-1)s(-1) and k (2) = (2.1 +/- 0.1) x 10(-12) cm3molecule(-1)s(-1). The Arrhenius expressions from our results are (units in cm3molecule(-1)s(-1)): k (1) = (2.3 +/- 1.4) x 10(-10) exp - (2254 +/- 177)/T(234-315 K) and k (2) = (3.7 +/- 0.5) x 10(-11) exp - (852 +/- 38)/T(234-333 K) (errors are sigma). The reactions proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.88 +/- 0.09 and 0.95 +/- 0.10 (errors are 2sigma) were obtained for HFE-7100 and HFE-7200 reactions, respectively.     

Determination of intermediates and mechanism for soot combustion with NOx/O₂ on potassium-supported Mg-Al hydrotalcite mixed oxides by in situ FTIR

The soot combustion with NO(x) and/or O(2) on potassium-supported Mg-Al hydrotalcite mixed oxides under tight contact condition was studied using temperature-programmed oxidation (TPO), isothermal reaction and in situ FTIR techniques. The presence of NO(x) in O(2) favors the soot combustion at lower temperatures (<300 °C). However, a little suppression was observed at higher temperatures (>300 °C), which was accompanied by a substantial NO(x) reduction. The ketene (C═C═O) and isocyanate (NCO(-)) species were determined as the reaction intermediates. In NO(x) + O(2), NO(2) directly interacts with the free carbon sites (C═C*) through two parallel reactions: (1) NO(2) + C═C* → C═C═O + NO; (2) NO(2) + C═C* → NCO(-) + CO(2). The two reactions can proceed easily, which accounts for the promotion effect of NO(x) on soot combustion at lower temperatures. The further oxidation of NCO(-) by NO(2) or O(2) is responsible for the simultaneous reduction of NO(x). However, the reactions between NO(2) and C═C* are limited by the amount of free carbon sites, which can be provided by the oxidation of soot by O(2) at higher temperatures. The interaction of NO(x) and catalyst results in the formation of nitrates and nitrites, which poisoned the active K sites.     

Using bromine gas to enhance mercury removal from flue gas of coal-fired power plants

Bromine gas was evaluated for converting elemental mercury (Hg0) to oxidized mercury, a form that can readily be captured by the existing air pollution control device. The gas-phase oxidation rates of Hg0 by Br2 decreased with increasing temperatures. SO2, CO, HCl, and H2O had insignificant effect, while NO exhibited a reverse course of effect on the Hg0 oxidation: promotion at low NO concentrations and inhibition at high NO concentrations. A reaction mechanism involving the formation of van der Waals clusters is proposed to accountfor NO's reverse effect. The apparent gas-phase oxidation rate constant, obtained under conditions simulating a flue gas without flyash, was 3.61 x 10(-17) cm3 x molecule(-1) x s(-1) at 410 K corresponding to a 50% Hg0 oxidation using 52 ppm Br2 in a reaction time of 15 s. Flyash in flue gas significantly promoted the oxidation of Hg0 by Br2, and the unburned carbon component played a major role in the promotion primarily through the rapid adsorption of Br2 which effectively removed Hg0 from the gas phase. At a typical flue gas temperature, SO2 slightly inhibited the flyash-induced Hg0 removal. Conversely, NO slightly promoted the flyash induced Hg0 removal by Br2. Norit Darco-Hg-LH and Darco-Hg powder activated carbons, which have been demonstrated in field tests, were inferred for estimating the flyash induced Hg0 oxidation by Br2. Approximately 60% of Hg0 is estimated to be oxidized with the addition of 0.4 ppm of gaseous Br2 into full scale power plant flue gas.     

Performance of a sulfide-oxidizing, sulfur-producing membrane biofilm reactor treating sulfide-containing bioreactor effluent

Sulfide-containing waste streams are generated in mining, petrochemical plants, tanneries, viscose rayon manufacture, and the gasification of coal. Colorless sulfur bacteria can oxidize sulfide to elemental sulfur (S°), which can be recovered, when oxygen is their electron acceptor. This study evaluated sulfide oxidation and S° recovery in an oxygen-based membrane biofilm reactor (MBfR) treating the effluent from a sulfidogenic anaerobic baffled reactor. Sulfide oxidation efficiency (37-99%) and S° recovery (64-89% of oxidized sulfide) could be controlled by manipulating the sulfide loading, oxygen pressure to the fibers, and hydraulic retention time (HRT). For example, too-low oxygen pressure decreased S° recovery due to decreased sulfide oxidation, but too-high oxygen pressure lowered S° recovery due to its oxidation to sulfate. Most importantly, high sulfide oxidation (>98%) and conversion to S° (>75%) could be achieved together when the sulfide loading was less than 1.7 mol/m2·d and the O? pressure was sufficient to give an O? flux of at least 1.5 mol/m2·d. However, higher sulfide loading could be compensated by a higher O? pressure, and the best performance occurred when the sulfide loading was high (2 molS/m2·d), the O? pressure was high (～1 atm), and the HRT was short (1.9 h). Membrane fouling caused a low O? flux, which led to low sulfide-oxidation efficiency, but fouling could be reversed by mild acid washing.