Thermal destruction of benzene

The thermal destruction of benzene in methane/air flue gas is studied experimentally using an atmospheric laminar flow reactor in laboratory scale. The reactor is operated at four different fuel equivalent ratios (phi = 0.06, 0.1,0.5, 3.7), and temperatures in the range from 850 to 973 K and realises a residence time of 5 s. Stable-species concentrations are measured by gas chromatography (GC) and high-pressure liquid chromatography (HPLC), where phenol, acetylene, formaldehyde, acrolein, methane and acetaldehyde are the major hydrocarbon products besides CO and CO2. The augmentation of the temperature from 850 to 973 K increases the benzene conversion rate from 55% to 99%. The experimental results for one fuel equivalent ratio (phi = 0.5) are compared to the benzene model proposed by Emdee et al. (J. Phys. Chem. 92 (1992) 2151-2161). A fair agreement is observed for the benzene consumption and the CO production throughout the temperature range considered here. The small hydrocarbons are not very well matched, which requires further research on the sub-models. Our experimental results on laboratory scale provide a database for the modelling of benzene oxidation in waste incinerators.     

Mathematical model for photocatalytic destruction of organic contaminants in air

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO2 was selected to compare with the MTU-PtTiO2-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 degrees C. For toluene removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm2 and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 microg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

Enhanced Fenton's destruction of non-aqueous phase perchloroethylene in soil systems

The Fenton's system is applied to the destruction of perchloroethylene (PCE) present as a dense non-aqueous phase liquid (DNAPL) in soil slurry systems; the initial concentration of PCE was 45 times higher than its aqueous solubility. Studies were conducted in two matrices: Ottawa sand and soil from Warsaw, IN. In Ottawa sand, a 60-62% decrease in PCE concentration was observed, and Cl(-) recovery was 47-58%, whereas in Warsaw soil, a 44-49% decrease in PCE concentration and a Cl(-) recovery of 40-42% were observed after the addition of 600 mM H(2)O(2) and 10 mM dissolved iron. Significantly enhanced destruction resulted during application of N-(2-hydroxyethyl) iminodiacetic acid (HEIDA) to Warsaw soil. For example, in the absence of HEIDA in Warsaw soil, 36% PCE loss and 33% Cl(-) release were observed at 600 mM H(2)O(2) and 5 mM Fe(III), while 74% PCE loss and 63% Cl(-) release were achieved at 600 mM H(2)O(2) and 5 mM Fe(III)-HEIDA. For both soils, the catalytic activities of Fe(II) and Fe(III) were nearly equivalent. These findings clearly demonstrate that system design can be optimized with regard to process variables in Fenton's treatment of DNAPL in soils.     

VOC destruction by water diluted hydrogen mild combustion

This study represents a preliminary numerical evaluation of the effect of steam dilution and hydrogen addition on the oxidation of formaldehyde and benzene, chosen as representative of the volatile organic compounds (VOC), in mild condition by evaluating the autoignition time and the steady state attainment. These parameters are important in the design of thermal VOC destruction plants since they influence the abatement efficiency and, therefore, the plant dimension. It has come out that, in comparison with the system diluted in nitrogen, steam induces lower autoignition times and, on the other hand, longer times for the attainment of the steady state. In contrast, for very high water content the autoignition time slightly increases. In particular results have shown that is possible to identify an optimum value of steam content that allows for the attainment of the steady state condition by the lowest residence time. Hydrogen addition to systems diluted in nitrogen promotes the oxidation reactions and anticipates the steady state condition. In steam diluted systems hydrogen delays the autoignition of the mixtures even though anticipates the attainment of the complete destruction of the VOC. The rate of production analysis has showed that the H(2)/O(2) reactions, that promote the ignition and the destruction of VOC, are sensibly modified by the presence of water and hydrogen.     

Catalytic destruction of dichloromethane using perovskite-type oxide catalysts

Dichloromethane (DCM, also known as methylene chloride [CH2Cl2]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH2Cl2 by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH2Cl2 (Co = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O2 = 5-21%) influence the operational stability and capacity for the removal of CH2Cl2. The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH2Cl2 reduction was achieved by the catalytic oxidation over LaCoO3-based perovskite catalyst at 600 degrees C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH2Cl2 in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

High-temperature gas-phase formation and destruction of polychlorinated dibenzofurans

The high-temperature gas-phase decomposition of a PCB isomer was studied using a tubular flow reactor. The formation and destruction of various PCDFs were investigated in atmospheres containing different concentrations of O₂.     

Evidence for destruction of PCBs by the OH radical in urban atmospheres

Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.     

Thermal destruction of wastes containing polychlorinated naphthalenes in an industrial waste incinerator

A series of verification tests were carried out in order to confirm that polychlorinated naphthalenes (PCNs) contained in synthetic rubber products (Neoprene FB products) and aerosol adhesives, which were accidentally imported into Japan, could be thermally destroyed using an industrial waste incinerator. In the verification tests, Neoprene FB products containing PCNs at a concentration of 2800 mg/kg were added to industrial wastes at a ratio of 600 mg Neoprene FB product/kg-waste, and then incinerated at an average temperature of 985 °C. Total PCN concentrations were 14 ng/m³N in stack gas, 5.7 ng/g in bottom ash, 0.98 ng/g in boiler dust, and 1.2 ng/g in fly ash. Destruction efficiency (DE) and destruction removal efficiency (DRE) of congener No. 38/40, which is considered an input marker congener, were 99.9974 and 99.9995 %, respectively. The following dioxin concentrations were found: 0.11 ng-TEQ/m³N for the stack gas, 0.096 ng-TEQ/g for the bottom ash, 0.010 ng-TEQ/g for the boiler dust, and 0.072 ng-TEQ/g for the fly ash. Since the PCN levels in the PCN destruction test were even at slightly lower concentrations than in the baseline test without PCN addition, the detected PCNs are to a large degree unintentionally produced PCNs and does not mainly stem from input material. Also, the dioxin levels did not change. From these results, we confirmed that PCNs contained in Neoprene FB products and aerosol adhesives could be destroyed to a high degree by high-temperature incineration. Therefore, all recalled Neoprene FB products and aerosol adhesives containing PCNs were successfully treated under the same conditions as the verification tests.     

Ozone destruction by catalysis: Credibility of the threat

In an effort to assess the credibility of predictions concerning the O₃ layer and to pinpoint avenues for improving current stratospheric models, a review was undertaken of observational data believed to have a bearing on the validity of destruction of stratospheric O₃ by catalysis. Aside from short period responses of O₃ above 20 km to PCAs and changes in solar flux, no data were found to confirm catalytic destruction both qualitatively and quantitatively. Predicted changes following such perturbations as nuclear tests, solar cycle modulation of cosmic rays, PCA's and volcanic eruptions cannot be clearly identified in the total O₃ observations. Observed variations in total O₃ appear to have been controlled by processes not included in current stratospheric models. As a minimum, it is concluded that predictions regarding stratospheric O₃ do not, at present, warrant the confidence implied by CIAP.     

氧化物催化剂对非热等离子体催化降解甲苯的影响

考察了在干燥气氛下不同氧化物催化剂对非热等离子体催化降解甲苯的影响。从甲苯降解率、碳平衡、CO2选择性和O3去除4个方面,对比了氧化物催化剂的介电性能、表面供氧能力和比表面积与多孔结构对反应产生影响的强弱。结果表明,催化剂的介电性能有利于甲苯降解率、碳平衡和O3产量的提高,但对CO2选择性和O3去除的影响极小;一定能量密度下,催化剂比表面积与多孔结构对CO2选择性和O3去除所产生的影响要强于介电性能;催化剂表面供氧能力可明显促进反应的进行,其对反应所产生的影响要强于比表面积与多孔结构。     

Ultrasonic destruction of surfactants: application to industrial wastewaters.

This research focused on the use of sonication to destroy surfactants and surface tension properties in industrial wastewaters that affect traditional water treatment processes. We have investigated the sonochemical destruction of surfactants and a chelating agent to understand the release of metals from surfactants during sonication. In addition, the effects of physical properties of surfactants and the effect of ultrasonic frequency were investigated to gain an understanding of the factors affecting degradation. Sonochemical degradation of surfactants was observed to be more effective than nonsurfactant compounds. In addition, as the concentration is increased, the degradation rate constant does not decrease as significantly as with nonsurfactant compounds in the near-field acoustical processor reactor. The degradation of metal complexes is not as effective as in the absence of the metal. However, this is likely an artifact of the model complexing agent used. Surfactant metal complexes are expected to be faster, as they will accumulate at the hot bubble interface, significantly increasing ligand exchange kinetics and thus degradation of the complex.     

Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill

Mechanochemical destruction (MCD) has been recognized as a promising non-combustion technology for the disposal of obsolete pesticides belonging to the persistent organic pollutants (POPs). Mirex, a termiticide ever used for many years in China, was ball milled in the presence of various reagent(s) in a planetary ball mill at room temperature to investigate the destruction efficiency. The ground samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, gas chromatography (GC), and ion chromatography (Martins, Bicego et al.). Under the same conditions of mill rotary rate and charge ratio, the mixture of iron powder and quartz sand (Fe/SiO₂) was found best in promoting the mirex destruction. Mirex was completed destroyed after 2 h grinding at a charge ratio of 36:1 (reagent/mirex, m/m) and a mill rotation speed of 550 rpm. No organic compound was detected by GC/μECD screening. The yield of water-soluble chlorine determined by ion chromatography (Martins, Bicego et al.) in the final residue accounted for 90.7% of chlorine in the original mirex, which indicated a nearly complete dechlorination. Signals of both graphite and amorphous carbon were found in the Raman spectra of the co-ground powder samples. With the main final degradation products of water soluble Cl and carbon, the mechanism of the mechanochemical destruction approach should be dechlorination followed by the carbonization.     

Combustion and thermal destruction of hexanes in the presence of inorganic and organic chlorine

Hexane was burned in an atmosphere containing an equal molar quantity of hydrogen chloride. Combustion characteristics and partial combustion products were compared to the combustion of pure 1-chlorohexane in air. The product distribution and burning properties were nearly identical.     

Impact of ozone mini-holes on the heterogeneous destruction of stratospheric ozone

A comprehensive study of ozone mini-holes over the mid-latitudes of both hemispheres is presented, based on model simulations with the coupled climate-chemistry model ECHAM4.L39(DLR)/CHEM representing atmospheric conditions in 1960, 1980, 1990 and 2015. Ozone mini-holes are synoptic-scale regions of strongly reduced total ozone, directly associated with tropospheric weather systems. Mini-holes are supposed to have chemical and dynamical impacts on ozone levels. Since ozone levels over northern mid-latitudes show a negative trend of approximately -4%/decade and since it exists a negative correlation between total column ozone and erythemally active solar UV-radiation reaching the surface it is important to understand and assess the processes leading to the observed ozone decline. The simulated mini-hole events are validated with a mini-hole climatology based on daily ozone measurements with the TOMS (total ozone mapping spectrometer) instrument on the satellite Nimbus-7 between 1979 and 1993. Furthermore, possible trends in the event frequency and intensity over the simulation period are assessed. In the northern hemisphere the number of mini-hole events in early winter decreases between 1960 and 1990 and increases towards 2015. In the southern hemisphere a positive trend in mini-hole event frequency is detected between 1960 and 2015 in spring associated with the increasing Antarctic Ozone Hole. Finally, the impact of mini-holes on the stratospheric heterogeneous ozone chemistry is investigated. For this purpose, a computer-based detection routine for mini-holes was developed for the use in ECHAM4.L39(DLR)/CHEM. This method prevents polar stratospheric cloud formation and therefore heterogeneous ozone depletion inside mini-holes. Heterogeneous processes inside mini-holes amount to one third of heterogeneous ozone destruction in general over northern mid- and high-latitudes during winter (January-April) in the simulation.     

Rapid reductive destruction of hazardous organic compounds by nanoscale Fe0

Fe0-mediated reductive destruction of hazardous organic compounds such as chlorinated organic compounds (COCs) and nitroaromatic compounds (NACs) in the aqueous phase is one of the latest innovative technologies. In this paper, rapid reductive degradation of COCs and NACs by synthesized nanoscale Fe0 in anaerobic batch systems was presented. The nanoscale Fe0, characterized by high specific surface area and high reactivity, rapidly transformed trichloroethylene (TCE), chloroform (CF), nitrobenzene (NB), nitrotoluene (NT), dinitrobenzene (DNB) and dinitrotoluene (DNT) under ambient conditions, which results in complete disappearance of the parent compounds from the aqueous phase within a few minutes. GC analysis reported that the main products of the dechlorination of TCE and CF were ethane and methane as well as that most of the nitro groups in NACs were reductively transformed to amine groups. These results suggest that the rapid reductive destruction by nanoscale Fe0 is potentially a viable in situ or aboveground treatment of groundwater contaminated with hazardous organic compounds including COCs and NACs.     

Formation and destruction of PCDD/F inside a grate furnace

Formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans PCDD/F during the combustion process was investigated experimentally in a pilot plant. All important process steps like the burnout of the fuel bed on the grate, the burnout of the flue gas inside the combustion chamber, the heat recovery in a boiler as well as influences of the fuel composition are described in detail.

High concentrations especially of PCDF are formed during the burnout of the fuel bed. The formation reaction is mainly influenced by the fuel composition and the burnout characteristic of the fuel bed. Fuels with low chlorine and low metal content (Cu) result only in negligible concentrations of PCDD/F.

Under stable combustion conditions characterized by an excellent flue gas burnout PCDD/F will almost be completely destroyed already inside the combustion chamber. “Cold strands” of unburned flue gas (high CO concentrations) caused by disturbed combustion conditions will result in high concentrations of PCDD and especially of PCDF in the raw gas.

A second place of PCDD/F formation is the well-known boiler section. Here fly ash deposits containing residual carbon (mainly soot particles) are the source for the formation reaction. Under stationary effective combustion conditions, they are dominant for PCDD/F concentrations in the raw gas over a very long period of time.

Stationary efficient flue gas burnout (especially soot) together with effective boiler cleaning will guaranty low concentrations of PCDD/F in the flue gas in front of the flue gas cleaning system.     

Synergistic effects of combination of photolysis and ozonation on destruction of chlorophenols in water.

Synergistic effects including TOC elimination, ozone consumption and microtoxicity reduction for combination of photolysis and ozonation compared to those of direct photolysis and ozonation alone on destruction of chlorophenols including 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol were studied. It was found that the synergistic effects of combination of photolysis and ozonation increased obviously with increasing initial pH of solution to basic pH levels. Results showed that the synergistic effects of photolytic ozonation under the conditions imposed was notable with mineralization rate enlarging more than 100%, oxidation index (OI) decreasing 50%, and microtoxicity being reduced by 30%, indicating that the potentialities of photolytic ozonation compared to direct photolysis and ozonation alone was remarkable for treatment of industrial wastewater containing chlorophenols.     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.     

介质阻挡放电-催化降解空气中甲苯的研究

着重考察了催化剂分解O3对介质阻挡放电-催化降解甲苯效果的影响,对比不同催化剂在3种催化剂结合方式下对O3分解能力及甲苯降解效果.同时研究了影响O3,产生及分解的条件--放电电压、水汽和氧含量对甲苯降解的影响.结果表明,催化剂的O3分解能力越强,对甲苯的降解效果越好,O3的催化分解在甲苯降解过程中起重要作用.当放电电压为10 kv时,在余辉区和等离子体区加入催化剂,甲苯的去除率分别由无催化剂时候的33.8%提高到55.6%～66.2%和65.2%～74.2%.气流中的水汽对O3的产生和分解都产生不利影响,可降低甲苯的去除率.氧气含量高时,一方面增加O3的产生,另一方面降低催化剂对O3的分解,在O3含量为5%时,甲苯去除效果较佳.