Regenerative Thermal Oxidation of Airborne N,N-Dimethylformamide and Its Associated Nitrogen Oxides Formation Characteristics

Abstract

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NO_x) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m × 0.14 m × 1 m (L × W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (t _s) of 1.5 min, a superficial gas velocity (U _g) of 0.39 m/sec (evaluated at an influent air temperature of around 30 °C) and preset maximum destruction temperatures (T _S) of 750–950 °C, no NO_x was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N?m³. The “NO_x-N formation/DMF-N destruction” mass ratios were in the range 0.76–1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO_x formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NO_x formation ratios were in the range 0.75–0.96. The TRE decreased as U _g increased but was invariant with T _s. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Performance characteristics of a regenerative catalytic oxidizer for treating VOC-contaminated airstreams

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. x 200-cm height regenerative beds was used to treat methyl ethyl ketone (MEK) and toluene, respectively, in an airstream. The regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m2/m3, and specific heat capacity 840 J/kg degree C) as a solid regenerative material and K-type thermal couples for measuring solid and gas temperatures, respectively. The catalyst bed temperature was kept around 400 degrees C and the gas superficial velocity was operated at 0.234 m/sec. This investigation measured and analyzed distributions of solid and gas temperatures with operating time and variations of volatile organic compound (VOC) concentrations in the regenerative beds. The overall VOC removal efficiency exceeded 98% for MEK and 95% for toluene. Degradation of VOCs will exist for MEK on the surface of solid material (gravel) in the temperature range of 330-400 degrees C, but toluene does not exhibit this phenomenon.     

Performance Characteristics of a Regenerative Catalytic Oxidizer for Treating VOC-Contaminated Airstreams

ABSTRACT

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. × 200-cm height regenerative beds was used to treat methyl ethyl ketone (MEK) and toluene, respectively, in an airstream. The regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m²/m³, and specific heat capacity 840 J/kg °C) as a solid regenerative material and K-type thermal couples for measuring solid and gas temperatures, respectively. The catalyst bed temperature was kept around 400 °C and the gas superficial velocity was operated at 0.234 m/sec. This investigation measured and analyzed distributions of solid and gas temperatures with operating time and variations of volatile organic compound (VOC) concentrations in the regenerative beds. The overall VOC removal efficiency exceeded 98% for MEK and 95% for toluene. Degradation of VOCs will exist for MEK on the surface of solid material (gravel) in the temperature range of 330-400 °C, but toluene does not exhibit this phenomenon.     

Bio-oxidation of airborne volatile organic compounds in an activated sludge aeration tank

An activated sludge aeration tank (40 x 40 x 300 cm, width x length x height) with a set of 2-mm orifice air spargers was used to treat gas-borne volatile organic compounds (VOCs; toluene, p-xylene, and dichloromethane) in air streams. The effects of liquid depth (Z), aeration intensity (G/A), the overall mass-transfer rate of oxygen in clean water (KLaO2), the Henry's law constant of the tested VOC (H), and the influent gaseous VOC concentration (C0) on the efficiency of removal of VOCs were examined and compared with a literature-cited model. Results show that the measured VOC removal efficiencies and those predicted by the model were comparable at a G/A of 3.75-11.25 m3/m2 hr and C0 of approximately 1000-6000 mg/m3. Experimental data also indicated that the designed gas treatment reactor with KLaO2 = 5-15 hr(-l) could achieve > 85% removal of VOCs with H = 0.24-0.25 at an aerated liquid depth of 1 m and > 95% removal of dichloromethane with H = 0.13 at a 1-m liquid depth.     

Kinetics of catalytic oxidation of benzene, n-hexane, and emission gas from a refinery oil/water separator over a chromium oxide catalyst

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr2O3) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300-14,700 mg/m3 and 240-400 degrees C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained. Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results. In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr2O3 catalyst.     

DOC系统催化性能的仿真和分析

以 Langmuire Hinshelwood机理为理论依据,基于MATLAB/Simulink 建立DOC系统的数值计算模型,研究不同参数(如空速、氧气浓度、NO2/NOx比例)对氮氧化物（NOx）、一氧化碳（CO）、碳氢化合物（HC）转化效率的影响, 并对部分工况进行了实验研究,从而验证数值模型的准确性。结果表明,空速的降低可以增大DOC对CO、HC、NO的氧化性能,这是由于排气在催化器内的反应时间增长。当排气温度为225～300 ℃时,减小空速对增大HC的氧化效率效果明显,当排气温度在175～450 ℃范围内,减小空速对增大NO的氧化效率影响明显;当O2浓度低于1%,排气温度在175～250 ℃时,CO转化效率增大,在250 ℃之后均接近100%。当O2浓度为10%时,温度的变化对CO的转化效率影响很小。当O2浓度大于1%时,温度的变化对NO的氧化效率影响较大;当排气温度在300～550 ℃时,NO2/NOx比例的变化对NO的转化效率影响较大。降低排气中NO2/NOx比例,能够在排气温度高于300 ℃时,明显提高NO的转化效率。     

蓄热式氧化炉在无机材料煅烧尾气处理中的应用

分子筛煅烧尾气中含有三乙胺、正丁胺等挥发性有机化合物（VOCs）,严重影响厂区及周边环境。为彻底治理有机废气污染,采用三床式蓄热式氧化炉（RTO）处理有机废气,通过优化调整控制工艺,以排烟温度控制法替代原有的排烟时间控制法。结果表明：排烟温度控制法可确保排烟温度保持在设计范围内,有效降低了排烟热损失;蓄热式氧化炉通过吸热-燃烧-放热周期性稳定运行,在天然气平均耗量4.5 m3·h-1的情况下,获得99%以上的VOCs去除效率,达到预期目标。蓄热式氧化法是一种经济、高效、稳定和安全的有机废气处理技术。     

Bioconversion of Dimethylformamide in Biofilters

ABSTRACT

Bioconversion of dimethylformamide (DMF) was studied using two sets of three-stages-in-series biofilters, one packed with inoculated pig manure and the other with coconut fiber compost-based media. The two media were different in carbon/nitrogen (C/N) ratio and specific area. Tests were made to compare effects of different C/N ratio and specific area on the performance of the filter and on the variation of physicochemical properties of the media for treating DMF. DMF concentration in the influent air stream was in the range of 100 to 4,500 mg/m³. The gas retention time (GRT) in the first stages of both filters was 19 to 76 sec. The volumetric loading of DMF (L) to the first stages of both filters was 3 to 97 g DMF-N/m³.h (15.6 to 506 g DMF/m³.h). Results indicated that DMF was successively hydrolyzed to ammonia and nitrified to nitrite and nitrate or incorporated into microbial cell. Inlet portions of the media subjected to high DMF or ammonia loading varied greatly in pH due to insufficient buffering capacity. The middle portions of the media subjected to moderate ammonia loading were suitable for nitrification. The coconut fiber compost media with a higher initial C/ N ratio and porosity favored the elimination of DMF. For the media, DMF-N removal efficiencies of larger than 90% were obtained with L < 50 g DMF-N/m³.h and GRT > 23 sec. The pig manure compost media with a lower initial C/N ratio favored the nitrification reaction; its maximum capacity was 8.58 g NO₃ ^--N/m³.h.     

A comparative study in treating two VOC mixtures in trickle bed air biofilters

Two independent parallel trickling bed air biofilters (TBABs) ("A" and "B") with two different typical VOC mixtures were investigated. Toluene, styrene, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK) were the target VOCs in the mixtures. Biofilter "A" was fed equal molar ratio of the VOCs and biofilter "B" was fed a mixture based on EPA 2003 emission report. Backwashing and substrate starvation operation were conducted as biomass control. Biofilter "A" and "B" maintained 99% overall removal efficiency for influent concentration up to 500 and 300 ppmv under backwashing operating condition, respectively. The starvation study indicated that it can be an effective biomass control for influent concentrations up to 250 ppmv for biofilter "A" and 300 ppmv for "B". Re-acclimation of biofilter performance was delayed with increase of influent concentration for both biofilters. Starvation operation helped the biofilter to recover at low concentrations and delayed re-acclimation at high concentrations. Furthermore, re-acclamation for biofilter "B" was delayed due to its high toluene content as compared to biofilter "A". The pseudo first-order removal rate constant decreased with increase of volumetric loading rate for both biofilters. MEK and MIBK were completely removed in the upper 3/8 media depth. While biofilter depth utilization for the removal of styrene and toluene increased with increase of influent concentrations for both biofilters. However, toluene removal utilized more biofilter depth for biofilter "B" as compared to biofilter "A".     

A fungal vapor-phase bioreactor for the removal of nitric oxide from waste gas streams.

Ground-level O3 formation is becoming a major concern in many cities due to recent tightening of O3 regulations. To control O3 formation, more efficient treatment processes for O3 precursors, such as NOx and volatile organic compounds (VOCs), are needed. One promising new technology for removing both NOx and VOCs from off-gas streams is biofiltration, a simple process whereby contaminated air is passed through a biologically active packed bed. In this study, a toluene-degrading fungal bioreactor was used to treat an aerobic gas stream contaminated with NO. The fungal bioreactor removed 93% of the inlet 250-ppmv NO at an empty bed contact time (EBCT) of 1 min when supplied with 90 g/m3/hr toluene. The presence of NH4+ concentrations greater than 0.4 mg NH3/g dry packing medium, however, resulted in poor NO removal. The bioreactor achieved a maximum toluene elimination capacity of 270 g/m3/hr and maintained greater than 95% toluene removal efficiencies over the 175-day study period.     

尿素/三乙醇胺吸收烟气NO_x的实验研究

以尿素作为吸收液,与NOx反应生成N2和CO2,脱除烟气中的氮氧化物。以一套双级串连的填料塔为主体反应器,分别对气速、液气比、反应物浓度、添加剂浓度和反应温度等参数对尿素溶液吸收NOx反应的影响进行了实验研究,获得了优化实验工况,研究结果显示,在气速为0.1 m/s、液气比为16 L/m3、三乙醇胺为0.01%（质量比）、尿素浓度为13%（质量比）工况下,反应温度为30~70℃,脱硝总效率可达50%以上,且随着NOx体积分数增加而提高。     

The annual course of TCA formation in the lower troposphere: a modeling study

We present a modeling study investigating the influence of climate conditions and solar radiation intensity on gas-phase trichloroacetic acid (TCA) formation. As part of the ECCA-project (Ecotoxicological Risk in the Caspian Catchment Area), this modeling study uses climate data specific for the two individual climate regimes, namely "Kalmykia" and "Kola Peninsula". A third regime has also been included in this study, namely "Central Europe", which serves as a reference to somehow more moderate climate conditions. The simulations have been performed with a box modeling package (SBOX, photoRACM), which uses Regional Atmospheric Chemistry Mechanism (RACM) as its chemistry scheme. For this model a mechanism supplement has been developed including the reaction pathways of methyl chloroform photooxidation. The investigations are completed by a detailed sensitivity study addressing the impact of temperature and relative humidity. Atmospheric OH and HO2 concentrations and the NOx/HO2 ratio were identified as the governing quantities controlling the TCA formation trough methyl chloroform oxidation in the gas phase. Model calculations show a TCA production rate ranging between almost zero and 6.5 x 10(3) molecules cm(-3) day(-1) depending on location and season. In the Kalmykia regime the model predicts mean TCA production rates of 1.3 x 10(-4) and 5.4 x 10(-5) microg m(-3) year(-1) for the urban and rural environment, respectively. From the comparison of model calculations with measured TCA burdens in the soil ranging between 130 g m(-3) and 1750 g m(-3) we conclude that TCA formation through methyl chloroform photooxidation in the gas-phase is probably not the principal atmospheric TCA source in this region.     

Treatment of N,N-dimethylacetamide waste gas by a trickle-bed air biofilter.

The system performance of a trickle-bed air biofilter (TBAB) for treating N,N-dimethylacetamide (DMAC) waste gas was investigated under different gas flow rates and influent concentrations. In the pseudo-steady-state conditions, the DMAC elimination capacity increased but the removal efficiency decreased as the influent loading increased. More than 90% and 80% DMAC removal efficiencies are achieved for influent loadings below 20.2 and 34.5 g DMAC/m3/h, respectively. The TBAB appears to be an effective treatment process for controlling DMAC emission with low-to-medium loadings and the effectiveness could be maintained over a long-period operation.     

水泥分解炉掺烧干污泥对NOx排放的影响

针对水泥窑炉NOx排放问题,提出了在分解炉上采用掺烧干污泥对烟气进行脱硝的方法。通过在水泥分解炉进行实验,研究了掺烧干污泥对NOx的影响。实验表明,在保持CO浓度和含氧量在一定范围内相对不变的条件下,NOx浓度随着干污泥掺烧量增加而减少。在保持干污泥掺烧量、CO浓度在一定范围内相对不变的情况下,NOx排放浓度随着含氧量的增加而增加,表明在富氧环境下,NOx比较容易生成。在保持干污泥掺烧量、含氧量不变的情况下,NOx排放浓度随着CO浓度的增加而减少,说明在高温环境下,干污泥暴露在烟气中的碳不断与氧反应,加快了干污泥活性炭化的进程,并促使NOx不断被吸附。同时,NOx生成所需的氧被碳原子掠夺,从而使CO浓度增加,并抑制了NOx的生成。     

Performance of a semi-industrial scale gasification process for the destruction of polychlorinated biphenyls

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spectrometry. The coplanar PCBs congeners 77, 105, 118, 156/ 157, and 167 were detected in the syngas at concentrations < 2 x 10(-7) mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was > 99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 x 10(-6) ng-toxic equivalent (TEQ)/m3 and 7.1 x 10(-6) ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Oxidative co-treatment using hydrogen peroxide with anaerobic digestion of excess municipal sludge.

The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H2O2). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H2O2/g influent volatile suspended solids (VSS(influent)). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H2O2/g VSS(influent)). Surprisingly, for 1.0 g H2O2/g VSS(influent), only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process.     

Treatment of ethylether in air stream by a biotrickling filter packed with slags.

This paper reports results of studies using a biotrickling filter with blast-furnace slag packings (sizes = 2-4 cm and specific surface area = 120 m2/m3) for treatment of ethylether in air stream. Effects of volumetric loading, superficial gas velocity, empty bed gas retention time, recirculation liquid flow rate, and biofilm renewal on the ethylether removal efficiency and elimination capacity were tested. Results indicate that ethylether removal efficieincies of more than 95% were obtained with an empty bed retention time (EBRT) of 113 sec and loadings of lower than 70 g/m3/hr. At an EBRT of 57 sec, removal efficiencies of more than 90% could only be obtained with loadings of lower than 35 g/m3/hr. The maximum elimination capacities were 71 and 45 g/m3/hr for EBRT = 113 and 57 sec, respectively. The maximum ethylether elimination capacities were 71 and 96 g/m3/hr, respectively, before and after the renewal at EBRT = 113 sec. With an EBRT of 113 sec and a loading of lower than 38 g/m3/hr, the removal efficiency was nearly independent of the superficial liquid recirculation velocity in the range of 3.6 to 9.6 m3/m2/hr. From data regression, simplified masstransfer limited, and reaction- and mass-transfer limited models correlating the contaminant concentration and the packing height were proposed and verified. The former model is applicable for cases of low influent contaminant concentrations or loadings, and the latter is applicable for cases of higher ones. Finally, CO2 conversion efficiencies of approximately 90% for the influent ethylether were obtained. The value is comparable to data reported from other related studies.     

Kinetics of Catalytic Oxidation of Benzene,n-Hexane,and Emission Gas from a Refinery Oil/Water Separator over a Chromium Oxide Catalyst

ABSTRACT

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr₂O₃) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300–14,700 mg/m³ and 240–400 ° C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained.

Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results.

In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr₂O₃ catalyst.     

Nitrogen oxides from waste incineration: control by selective non-catalytic reduction

An experimental study of the selective non-catalytic reduction (SNCR) process was carried out to determine the efficiency of NOx removal and NH3 mass balance, the NOx reducing reagent used. Experimental tests were conducted on a full-scale SNCR system installed in a hospital waste incineration plant. Anhydrous NH3 was injected at the boiler entrance for NOx removal. Ammonia was analyzed after each flue-gas treatment unit in order to establish its mass balance and NH3 slip in the stack gas was monitored as well. The effective fraction of NH3 for the thermal NOx reduction was calculated from measured values of injected and residual NH3. Results show that a NOx reduction efficiency in the range of 46.7-76.7% is possible at a NH3/NO molar ratio of 0.9-1.5. The fraction of NH3 used in NOx removal was found to decrease with rising NH3/NO molar ratio. The NH3 slip in the stack gas was very low, below permitted limits, even at the higher NH3 dosages used. No direct correlation was found between the NH3/NO molar ratio and the NH3 slip in the stack gas since the major part of the residual NH3 was converted into ammonium salts in the dry scrubbing reactor and subsequently collected in the fabric filter. Moreover, another fraction of NH3 was dissolved in the scrubbing liquor.