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.     

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.     

Removal of volatile and semivolatile organic contamination from soil by air and steam flushing

A soil core, obtained from a contaminated field site, contaminated with a mixture of volatile and semivolatile organic compounds (VOC and SVOC) was subjected to air and steam flushing. Removal rates of volatile and semivolatile organic compounds were monitored during flushing. Air flushing removed a significant portion of the VOC present in the soil, but a significant decline in removal rate occurred due to decreasing VOC concentrations in the soil gas phase. Application of steam flushing after air flushing produced a significant increase in contaminant removal rate for the first 4 to 5 pore volumes of steam condensate. Subsequently, contaminant concentrations decreased slowly with additional pore volumes of steam flushing. The passage of a steam volume corresponding to 11 pore volumes of steam condensate reduced the total VOC concentration in the soil gas (at 20 degrees C) by a factor of 20 to 0.07 mg/l. The corresponding total SVOC concentration in the condensate declined from 11 to 3 mg/l. Declines in contaminant removal rates during both air and steam flushing indicated rate-limited removal consistent with the persistence of a residual organic phase, rate-limited desorption, or channeling. Pressure gradients were much higher for steam flushing than for air flushing. The magnitude of the pressure gradients encountered during steam flushing for this soil indicates that, in addition to rate-limited contaminant removal, the soil permeability (2.1 x 10(-9) cm2) would be a limiting factor in the effectiveness of steam flushing.     

Airflow Related to Denver Air Pollution

A continuous process for the disposal of halogen-containing organic residues has been developed. This process is based on the decomposition of wastes into gaseous byproducts by high temperature reactions with air and steam. The exit gases, which are essentially carbon dioxide, nitrogen, and hydrogen halides, can be scrubbed with water, thereby completely eliminating atmospheric pollution.

A unique refractory-lined recuperative heat furnace has successfully operated in this fashion to dispose of more than 20 million pounds of liquid residues (average decomposition: 60% Cl₂; 35% carbon; and the remainder oxygen, hydrogen, and others) during the last year.

This process is cheaper than most conventional disposal methods (i.e., ground burial) and offers the added advantage of complete and permanent disposal.     

宽叶香蒲表面流人工湿地脱氮除磷效果研究

以运行A/O工艺的生化反应器出水为处理对象,在中试规模上研究了宽叶香蒲表面流人工湿地的脱氮除磷效果及影响因素.结果表明,在工况Ⅰ条件下,COD去除率为43.2%,COD面积负荷去除率为4.79 g/(m2·d),COD面积负荷去除率常数为0.18 m/d,SS、NH4+-N和NO-3-N的去除率分别为41.2%、9.4%、3.4%,TN去除率为11.8%,TN面积负荷去除率为1.36g/(m2·d),TN面积负荷去除率常数为0.04 m/d,TP去除率为30.1%,TP面积负荷去除率为0.29 g/(m2·d),TP面积负荷去除率常数为0.13 m/d;在工况Ⅱ条件下,COD去除率为18.7%,COD面积负荷去除率为1.19 g/(m2·d),COD面积负荷去除率常数为0.06 m/d,SS、NH4+-N、NO2--N、NO3--N的去除率分别为31.6%、29.8%、65.0%,29.2%.TN去除率为31.4%,TN面积负荷去除率为2.33 g/(m2·d),TN面积负荷去除率常数为0.12 m/d,TP去除率为29.4%,TP面积负荷去除率为0.22 g/(m2·d),TP面积负荷去除率常数为0.11 m/d.在COD面积负荷去除率,TN面积负荷去除率、TP面积负荷去除率分别为4.90～9.80、2.76～8.83、0.57～1.39 g/(m2·d),水力停留时间(HRT)为0.4～1.1 d条件下,随HRT,水温、(NO2+-N+NO3--N)/TN的增加,表面流人工湿地的TN面积负荷去除率线性增加.     

水碳比变化对汽油氧化重整制氢影响的研究

本文用正辛烷代替汽油从理论和实验两方面研究了水碳比变化对汽油氧化重整制氢反应的影响。理论研究表明 ,在绝热反应条件下 ,对应确定的反应温度存在一个最佳的氧油比及水碳比 ;实验研究表明 ,在非绝热反应体系中 ,在一定的氧油比及反应温度条件下 ,反应体系的转化率及生成氢的选择性均随水碳比的增加而增加 ,为实现燃料电池汽油制氢自热反应 ,反应体系应在一定水碳比条件下进行 ,实验条件下最佳的水碳比范围是 1.5— 2 .5之间。     

A Field Demonstration of the UV/Oxidation Technology to Treat Ground Water Contaminated with VOCs

This paper presents the Geld evaluation results of the ultraviolet radiation (UV)/oxidation technology developed by Ultrox International, Santa Ana, California. The Geld evaluation was performed at the Lorentz Barrel and Drum (LB&D) site in San Jose, California, under the Superfund Innovative Technology Evaluation program in February and March of 1989.

The UV/oxidation technology uses UV radiation, ozone, and hydrogen peroxide to oxidize organic contaminants present in water. At the LB&D site, this technology was evaluated in treating ground water contaminated with volatile organic compounds (VOCs). The Ultrox system achieved VOC removals greater than 90 percent. Most VOCs were removed through chemical oxidation. However, for a few VOCs, such as 1, 1, 1-trichloroethane and 1, 1-dichloroethane, stripping also contributed toward removal. The treated ground water met the applicable discharge standards for discharge into a local waterway at 95 percent confidence level. There were no harmful air emissions to the atmosphere from the Ultrox system, which is equipped with an off-gas treatment unit.     

Nitrification in natural waters with high suspended-solid content--a study for the Yellow River

In this research, the mechanism regarding the effects of suspended solids on nitrification in freshwater systems with high solid contents was examined. Experimental studies were conducted for natural water of the Yellow River under laboratory conditions. Nitrification kinetics was investigated in water systems with various levels of suspended-solid contents. The associated mechanisms were analyzed through investigation of the adsorption-desorption of ammonium nitrogen, the process of bacteria growth, and the feature of nitrification kinetics. The results indicated that the presence of suspended solids could accelerate the nitrification process. The nitrification rate would increase non-linearly with the increase of suspended-solid content. When the initial concentration of ammonia nitrogen was 12.70 mg/l in the water system, the ratios of half-time duration for nitrification would be 1.88:1.23:1 under suspended-solid contents of 0, 1.84 and 5.00 g/l, respectively. When the initial concentration of ammonia nitrogen was around 1.0 mg/l in the water system, the nitrification rates in systems with suspended-solid contents of 1.81 and 3.42 g/l would then be approximately 9 and 12 times that without suspended solids, respectively. The populations of nitrifying bacteria would rise with increasing suspended-solid content. The existence of suspended solids would increase the contact chances between bacteria and nitrogen, resulting in accelerated nitrification processes; this was manifested by the increased K(4) (tau(max)/K(S)) along with the raised suspended-solid contents while fitting nitrification kinetics with the growth-based logistic model. Since the amount of ammonium nitrogen adsorbed on suspended-solid surface was non-linearly proportional to the suspended-solid content, the nitrification rate was also non-linearly proportional to the suspended-solid content.     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Performance evaluation of the UV/H2O2 process on selected nitrogenous organic compounds: reductions of organic contents vs. corresponding C-, N-DBPs formations

The presence of various organic contaminants in water sources is of concern due to their direct threats to human health and potential to react with disinfectants to form carcinogenic byproducts including trihalomethanes, haloacetic acids and nitrosamines in finished water. This study applied both medium-pressure and low-pressure ultraviolet light coupled with hydrogen peroxide (UV/H₂O₂) to evaluate its efficacy for degradation of selected nitrogenous organic compounds and corresponding disinfection byproduct (DBP) formation. Six organic compounds were chosen as target precursors based on their nitrogen contents and molecular structures. The results showed that higher oxidation capacity resulted in better reduction of organic matters and DBP formation potentials (DBPFPs). However, insufficient contact time and oxidant doses could lead to a rise of DBPFPs in the early stages of UV/H₂O₂ reactions. A greater percentage removal was achieved for organic carbon than organic nitrogen after UV/H₂O₂ treatment, especially for compounds with complicated structure such as diltiazem. During the UV/H₂O₂ treatment, the intermediate products include tertiary amine, dimethyl amine (DMA) or DMA-like structures, which are N-nitrosodimethylamine (NDMA) precursors after chlorination or chloramination. Furthermore, it was observed that using dissolved organic nitrogen and DMA to predict NDMAFP could lead to biased conclusions because of the complex nature of nitrogenous matters in aqueous environments.     

Remediation of NAPL below the water table by steam-induced heat conduction

Previous experimental studies have shown that NAPL will be removed when it is contacted by steam. However, in full-scale operations, steam may not contact the NAPL directly and this is the situation addressed in this study. A two-dimensional intermediate scale sand box experiment was performed where an organic contaminant was emplaced below the water table at the interface between a coarse and a fine sand layer. Steam was injected above the water table and after an initial heating period the contaminant was recovered at the outlet. The experiment was successfully modeled using the numerical code T2VOC and the dominant removal mechanism was identified to be heat conduction induced boiling of the separate phase contaminant. Subsequent numerical modeling showed that this mechanism was insensitive to the porous medium properties and that it could be evaluated by considering only one-dimensional heat conduction.     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

An experimental and numerical study of the thermal oxidation of chlorobenzene

A combustion-driven flow reactor was used to examine the formation of chlorinated and non-chlorinated species from the thermal oxidation of chlorobenzene under post-flame conditions. Temperature varied from 725 to 1000 K, while the equivalence ratio was held constant at 0.5. Significant quantities of chlorinated intermediates, vinyl chloride and chlorophenol, were measured. A dominant C-Cl scission destruction pathway seen in pyrolytic studies was not observed. Instead, hydrogen-abstraction reactions prevailed, leading to high concentrations of chlorinated byproducts. The thermal oxidation of benzene was also investigated for comparison. Chemical kinetic modeling of benzene and chlorobenzene was used to explore reaction pathways. Two chlorobenzene models were developed to test the hypothesis that chlorobenzene oxidation follows a CO-expulsion breakdown pathway similar to that of benzene. For the temperatures and equivalence ratio studied, hydrogen abstraction by hydroxyl radicals dominates the initial destruction of both benzene and chlorobenzene. Chlorinated byproducts (i.e., chlorophenol and vinyl chloride) were formed from chlorobenzene oxidation in similar quantities and at similar temperatures to their respective analogue formed during benzene oxidation (i.e., phenol and ethylene).     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

Mineralization of phenol by Ce(IV)-mediated electrochemical oxidation in methanesulphonic acid medium: a preliminary study

The mediated electrochemical oxidation (MEO) process using cerium(IV) in methanesulphonic acid (MSA) as the oxidizing medium was employed for the mineralization of phenol in batch and continuous feeding modes. Although nitric acid was an extensively studied electrolyte for organic mineralization reactions in MEO processes it does possess the problem of NO(x) gas production during the reduction of nitric acid in the cathode compartment of the electrochemical cell. This problem could be circumvented by proper choice of the electrolyte medium such as MSA. The mediator cerium in MSA solution was first oxidized to higher oxidation state using an electrochemical cell. The produced Ce(IV) oxidant was then used for the destruction of phenol. It was found that phenol could be mineralized to CO2 by Ce(IV) in MSA. The evolved CO2 was continuously measured and used for the calculation of destruction efficiency. The destruction efficiency was observed to be 85% based on CO2 evolution for 1000 ppm phenol solution at 80 degrees C in continuous feed mode.     

Development of a reduced speciated VOC degradation mechanism for use in ozone models

A reduced mechanism to describe the formation of ozone from VOC oxidation has been developed, using the master chemical mechanism (MCM v2) as a reference benchmark. The ‘common representative intermediates’ (CRI) mechanism treats the degradation of methane and 120 VOC using ca. 570 reactions of ca. 250 species (i.e. the emitted VOC plus an average of about one additional species per VOC). It thus contains only ca. 5% of the number of reactions and ca. 7% of the number of chemical species in MCM v2, providing a computationally economical alternative. The CRI mechanism contains a series of generic intermediate radicals and products, which mediate the breakdown of larger VOC into smaller fragments (e.g., formaldehyde), the chemistry of which is treated explicitly. A key assumption in the mechanism construction methodology is that the potential for ozone formation from a given VOC is related to the number of reactive (i.e., C–C and C–H) bonds it contains, and it is this quantity which forms the basis of the generic intermediate groupings. Following a small degree of optimisation, the CRI mechanism is shown to generate levels of ozone, OH, peroxy radicals, NO and NO₂ which are in excellent agreement with those calculated using MCM v2, in simulations using a photochemical trajectory model applied previously to simulation of episodic ozone formation. The same model is used to calculate photochemical ozone creation potentials for 63 alkanes, alkenes, carbonyls and alcohols using both mechanisms. Those determined with the CRI mechanism show a variation from compound to compound which is remarkably consistent with that calculated with the detailed chemistry in MCM v2. This suggests that the CRI mechanism construction methodology is able to capture both the salient features of the ozone formation process in general, and how this varies from one VOC to another.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Improved vacuum-UV (VUV)-initiated photomineralization of organic compounds in water with a xenon excimer flow-through photoreactor (Xe2* lamp, 172 nm) containing an axially centered ceramic oxygenator

Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.     

Influence of phosphorus and trace metals in biofilters treating gaseous VOCs using a novel irrigation system

ABSTRACT

Although the appropriate supply of nutrients has been extensively researched, more information is required on the effects of nutrients in treating gaseous volatile organic compounds (VOCs) in biofiltration. In this study, the effects of phosphorous and trace metals on gaseous toluene and methyl ethyl ketone (MEK) removal were investigated. The transfer of nutrients from the irrigation liquid to the packed bed, and the consumption and holding amount of nutrients in the packing material were observed during biofiltration. Under conditions of 20–24 s of empty bed residence time, MEK removal was 95% or more in all conditions of the biofiltration reactors, whereas toluene removal was affected by the operating conditions of the reactors. Consumption ratio of phosphorus to carbon was from 1.7 × 10^?4 to 1.1 × 10^?3 in the steady state of VOC removal under the conditions of this study. When gaseous VOC treatment was restarted after nine days of shutdown, a significant decline in toluene removal was observed by the reactor in which phosphorus supply was approximately one fifth of the amount in another reactor. Two types of irrigation systems, soaking and spraying, were compared and soaking irrigation achieved a more even distribution of nutrients held inside the packed bed. Soaking irrigation was expected to lead to higher VOC removal capacity by this distribution effect of nutrients, but toluene removal in the reactor with this irrigation was lower than that in the reactor with spraying irrigation. One of the possible reasons for this was the inhibition of nutrients transfer in the bottom part of the reactor. The trend of transfer in all ingredients from the irrigation liquid to the packed bed was synchronized on the whole; however, this transfer relatively tended to be high in nitrate and sodium and low in ammonium and phosphate.

Implications: A major concern about using biofiltration systems to treat VOCs is the uncertainty regarding the appropriate nutrient supply to the filter bed to preserve microbial activity. This study showed that all the elements, except nitrogen, were retained sufficiently in the filter bed when a proper composition of nutrient solution was used for irrigation; however, phosphate addition may be needed when restarting a reactor from a prolonged period of shutdown. Distinct differences in the amount of transfer to the filter bed for different ingredients are probable, and may have to be taken into account when operating biofiltration reactors.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.