Performance of Copper Chloride-Impregnated Sorbents on Mercury Vapor Control in an Entrained-Flow Reactor System

Abstract

An entrained-flow system has been designed and constructed to simulate in-flight mercury (Hg) capture by sorbent injection in ducts of coal-fired utility plants. The test conditions of 1.2-sec residence time, 140 °C gas temperature, 6.7 m/sec (22 ft/sec) gas velocity, and 0–0.24 g/m³ (0–15 lbs of sorbent per 1 million actual cubic feet of flue gas [lb/MMacf]) sorbent injection rates were chosen to simulate conditions in the ducts. Four kinds of sorbents were used in this study. Darco Hg-LH served as a benchmark sorbent with which Hg control capability of other sorbents could be compared. Also, Darco-FGD was used as a representative raw activated carbon sorbent. Two different copper chloride-impregnated sorbents were developed in our laboratory and tested in the entrained-flow system to examine the possibility of using these sorbents at coal-fired power plants. The test results showed that one of the copper chloride sorbents has remarkable elemental mercury (Hg⁰) oxidation capability, and the other sorbent demonstrated a better performance in Hg removal than Darco Hg-LH.     

Comparison of seasonal phenol and p-cresol emissions from ground-level area sources in a dairy operation in central Texas

Although there are more than 200 odor-causing volatile organic compounds (VOCs), phenol and p-cresol are two prominent odor-causing VOCs found downwind from concentrated animal feeding operations (CAFOs). The VOC emissions from cattle and dairy production are difficult to quantify accurately because of their low concentrations, spatial variability, and limitations of available instruments. To quantify VOCs, a protocol following US. Environmental Protection Agency (EPA) Method TO-14A has been established based on the isolation flux chamber method and a portable gas chromatograph (GC) coupled with a purge-and-trap system. The general objective of this research was to quantify phenol and p-cresol emission rates (ERs) from different ground-level area sources (GLASs) in a free-stall dairy during summer and winter seasons using this protocol. Two-week-long sampling campaigns were conducted in a dairy operation in central Texas. Twenty-nine air samples were collected during winter and 37 samples were collected during summer from six specifically delineated GLASs (barn, loafing pen, lagoon, settling basin, silage pile, and walkway) at the free-stall dairy. Thirteen VOCs were identified during the sampling period and the GC was calibrated for phenol and p-cresol, the primary odorous VOCs identified. The overall calculated ERs for phenol and p-cresol were 2656 +/- 728 and 763 +/- 212 mg hd(-1) day(-1), respectively, during winter. Overall phenol and p-cresol ERs were calculated to be 1183 +/- 361 and 551 +/- 214 mg hd(-1) day(-1), respectively, during summer. In general, overall phenol and p-cresol ERs during winter were about 2.3 and 1.4 times, respectively, higher than those during summer.     

好氧颗粒污泥降解苯酚

以人工配水启动SBR,逐步提高进水苯酚浓度,探究好氧颗粒污泥对苯酚的降解能力,同时分析苯酚对好氧颗粒污泥特性的影响。经过55 d的运行,进水苯酚浓度逐渐增到3 000 mg/L,苯酚、COD及NH+4-N去除率分别达到了98.33%、97.27%和57.58%,好氧颗粒污泥表现出对苯酚的良好的去除能力。扫描电镜照片显示投加苯酚后的颗粒污泥表面更加光滑,结构更为紧凑。胞外聚合物红外光谱分析表明投加苯酚前后好氧颗粒污泥EPS的主要组分没有明显改变。苯酚毒性刺激了颗粒污泥分泌更多胞外聚合物,胞外聚合物中多糖含量由初始的12.70 mg/g VSS增加到35.17 mg/g VSS,蛋白含量由4.93 mg/g VSS增加到8.01 mg/g VSS。投加苯酚后的污泥粒径明显增大,主要污泥粒径由0.5~2.0 mm增大到2.0 mm以上。     

污泥含炭吸附剂对挥发性有机废气吸附实验研究

研究了污泥含炭吸附剂对挥发性有机污染物的吸附特性。结果表明,污泥含炭吸附剂对苯系物的吸附为典型的物理吸附,其吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;在吸附反应温度为20℃,气体流量为500 mL/m in(停留时间为0.424 s),甲苯浓度为2 700 mg/m3时,甲苯的饱和吸附容量为150.0 mg/g;同时,研究表明污泥含炭吸附剂对苯系物的饱和吸附容量和吸附强弱次序为二甲苯甲苯苯。结果表明污泥含炭吸附剂适合对中低浓度有机废气的吸附净化。     

Copper and trace element fractionation in electrokinetically treated methanogenic anaerobic granular sludge

The effect of electrokinetic treatment (0.15 mA cm(-2)) on the metal fractionation in anaerobic granular sludge artificially contaminated with copper (initial copper concentration 1000 mg kg(-1) wet sludge) was studied. Acidification of the sludge (final pH 4.2 in the sludge bed) with the intention to desorb the copper species bound to the organic/sulfides and residual fractions did not result in an increased mobility, despite the fact that a higher quantity of copper was measured in the more mobile (i.e. exchangeable/carbonate) fractions at final pH 4.2 compared to circum-neutral pH conditions. Also addition of the chelating agent EDTA (Cu2+:EDTA4- ratio 1.2:1) did not enhance the mobility of copper from the organic/sulfides and residual fractions, despite the fact that it induced a reduction of the total copper content of the sludge. The presence of sulfide precipitates likely influences the copper mobilisation from these less mobile fractions, and thus makes EDTA addition ineffective to solubilise copper from the granules.     

Copper chitosan nanocomposite: synthesis, characterization, and application in removal of organophosphorous pesticide from agricultural runoff

Purpose

Removal of malathion from agricultural runoff was studied using novel copper-coated chitosan nanocomposite (CuCH)??a biopolymeric waste obtained from marine industry.

Methods

Synthesis and characterization of the adsorbent using different spectral techniques like Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer, Emmett, and Teller surface analyzer have been carried out. Equilibrium studies have been carried out to optimize the dose rate, pH, and the reaction time. Parathion and methyl parathion removal were also evaluated by CuCH in the batch mode. Using gas chromatography?Cmass spectrometry (GC?CMS) and FTIR studies suitable mechanism for adsorption has been suggested.

Results

The particle size of the adsorbent ranged from 700 to 750?nm. The surface area was found to be 20?m²?g^-1 with a pore volume of 0.11?cc?g^-1. The maximum adsorption capacity of malathion by CuCH was found to be 322.6?±?3.5?mg?g^-1 at an optimum pH of 2.0. Presence of copper ions enhanced the adsorption capacity of the adsorbent. The reaction was found to follow pseudo second-order kinetics with a rate constant of 0.53?g?mg^-1?min^-1. Evidence from FTIR indicated that copper ions form a dithionate complex with malathion during the adsorption stage. The adsorbent was found to remove malathion completely from spiked concentration of 2?mg?l^-1 in the agricultural run-off samples. It was also found that CuCH removed other organophospurous pesticides like methyl parathion and parathion under prevailing conditions.

Conclusions

The results indicated that CuCH could be applied for the removal of organophosphorous pesticides.     

Adsorption/desorption of copper by a sandy soil amended with various rates of manure, sewage sludge, and incinerated sewage sludge

Organic amendments are sometimes applied to agricultural soils to improve the physical, chemical, and microbiological properties of the soils. The organic fractions in these soil amendments also influence metal reaction, particularly the adsorption and desorption of metals, which, in turn, determine the bioavailability of the metals and hence their phytotoxicities. In this study, a Quincy fine sandy (mixed, mesic, Xeric Torripsamments) soil was treated with 0 to 160 g kg(-1) rates of either manure, sewage sludge (SS), or incinerated sewage sludge (ISS) and equilibrated in a greenhouse at near field capacity moisture content for 100 days. Following the incubation period, the soil was dried and adsorption of copper (Cu) was evaluated in a batch equilibration study at either 0, 100, 200, or 400 mg L(-1) Cu concentrations in a 0.01M CaCl2 solution. The desorption of adsorbed Cu was evaluated by three successive elutions in 0.01M CaCl2. Copper adsorption increased with an increase in manure rates. At the highest rate of manure addition (160 g kg(-1) soil), Cu adsorption was two-fold greater than that by the unamended soil at all rates of Cu additions. With increasing rates of Cu additions, the adsorption of Cu decreased from 99.4 to 77.6% of Cu applied to the 160 g kg(-1) manure amended soil. The desorption of Cu decreased with an increase in rate of manure amendment. Effects of sewage sludge amendments on Cu adsorption were somewhat similar to those as described for manure additions. Likewise, the desorption of Cu was the least at the high rate of SS addition (160 g kg(-1)), although at the lower rates there was not a clear indication of the rate effects. In contrast to the above two amendments, the ISS amendment had the least effect on Cu adsorption. At the highest rate of ISS amendment, the Cu adsorption was roughly 50% of that at the similar rate of either manure or SS amendments, across all Cu rates.     

Individual and combined inhibition of phenol and thiocyanate on microbial activity of partial nitritation

This study evaluated the individual and interactive effect of phenol and thiocyanate (SCN⁻) on partial nitritation (PN) activity using batch test and response surface methodology. The IC₅₀ of phenol and SCN⁻ on PN sludge were 5.6 and 351 mg L⁻¹, respectively. The PN sludge was insensitive to phenol and SCN⁻ at levels lower than 1.77 and 43.3 mg L⁻¹, respectively. A regression model equation was developed and validated to predict the relative specific respiration rate (RSRR) of PN sludge exposed to different phenol and SCN⁻ concentrations. In the range of independent variables, the most severe inhibition was observed with a valley value (17%) for RSRR, when the phenol and SCN⁻ concentrations were 4.08 and 198 mg L⁻¹, respectively. An isobole plot was used to judge the combined toxicity of phenol and SCN⁻, and the joint inhibitory effect was variable depending on the composition and concentration of the toxic components. Furthermore, the toxic compounds showed independent effects, which is the most common type of combined toxicity.

     

An activated sludge process to reduce the pollution load of a dye-industry waste

A laboratory-scale activated sludge process was developed to reduce the pollution load of a dye-industry waste, containing aniline, phenol, methyl violet and rhodamine B as its major components. The waste exerted an organic load of 5576 mg litre(-1) as the chemical oxygen demand (COD), of 896 mg litre(-1) as total organic carbon (TOC), and had a 31.5 mg litre(-1) phenol content. A microbial sludge, capable of growing on the waste, was developed from cattle dung, adapted to the waste and used as a bioinoculum for the process. This resulted in reductions of 60% in COD, 37% in TOC, and 92% in phenol content, and a decrease in optical density of the colour of the waste from an initial 0.915 to 0.360 at 580 nm. Microorganisms isolated from sludge were identified as Pseudomonas alcaligenes and P. mendocina.     

微波法污水厂污泥制备活性炭的研究

研究了以污水厂污泥为原料、微波辐照下磷酸活化法制备污泥活性炭的工艺条件,探讨了微波功率、辐照时间以及磷酸浓度对活性炭碘值的影响.结果表明,微波功率480 W、辐照时间315 s、磷酸浓度40%～45%的条件下,制备的污泥活性炭碘值为301 mg/g,总孔孔容是0.37 mL/g,平均孔径8.8 nm,比表面积168 m2/g.将该污泥活性炭用于处理TNT红水,吸附效果良好.     

A New Method for the Rapid Determination of Volatile Organic Compound Breakthrough Times for a Sorbent at Concentrations Relevant to Indoor Air Quality

Abstract

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25% relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Seasonal patterns of non-terpenoid C6-C10 VOC emission from seven Mediterranean woody species

The seasonal pattern of non-terpenoid C6-C10 VOC emission by seven Mediterranean woody species (Bupleurum fruticosum, Cistus albidus, Pinus halepensis, Arbutus unedo, Erica arborea, Quercus coccifera, and Q. ilex) was studied under field conditions. Branch chamber samples were sorbed on carbotrap and analyzed by thermal desorption in combination with GC-MS. These non-terpenoid C6-C10 VOC emissions were large, almost of similar magnitude to those of terpenes. Overall, maximum values were recorded in spring and summer (up to 12 microg g(-1) DM h(-1) in Q. ilex) and minimum values in autumn and winter (up to 5 microg g(-1) DM h(-1) in Q. ilex). These C6-C10 VOC emissions represented 2.82% of the photosynthetic C fixation in summer and 0.22% in winter. Some compounds such as 2-ethoxyethyl acetate were emitted by most species, others such as 3-hexen-1-ol, phenol or decanal were significantly emitted only by few species. The greatest diversity of emitted non-terpenoid C6-C10 VOCs was observed in spring and in Q. ilex. Temperature seemed a strong driver of these seasonal changes but other species-specific and seasonal factors seem involved. These results indicate that C6-C10 non-terpenoid VOCs contribute a rather significant fraction of the total biogenic VOC flux from these Mediterranean species, especially in spring and summer, and therefore should be considered in VOC emission inventories and in model predictions of tropospheric chemistry.     

Breakthrough indicator for aromatic VOCs using needle trap samplers for activated carbon adsorbent

Internal circulation cabinets equipped with granular activated carbon (GAC) for adsorbing volatile organic compounds (VOCs) are widely used to store bottles containing organic solvents in universities, colleges, and hospital laboratories throughout Taiwan. This work evaluates the VOC adsorption capacities of GAC using various adsorption times for gas stream mixtures of 100 ppm toluene and 100 ppm o-xylene. Additionally, needle trap sampling (NTS) technology was used to indicate the time for renewing the GAC to avoid VOC breakthrough from adsorbents. Experimental results demonstrate that the proposed models can linearly express toluene and o-xylene adsorption capacities as the natural logarithm of adsorption time (ln(t)) and can accurately simulate the equilibrium adsorption capacities (Qe, g VOCs/g GAC) for gaseous toluene and o-xylene. The NTS, packed with 60-80 mesh divinylbenzene (DVB) particles, was compared in terms of extraction efficiency by simultaneously using the 75-microm Carboxen/polydimethylsiloxane-solid-phase microextraction (Carboxen/PDMS-SPME) fiber for time-weighted average (TWA) sampling, and experimental results indicated that the packed DVB-NTS achieved higher toluene extraction rates. Additionally, the NTS installed in the outlet air stream for adsorbing toluene and o-xylene exhausted through GAC accurately indicated toluene and o-xylene breakthrough times of 4700-5000 min. The GAC-NTS operational instructions to indicate the replacing time of adsorbent in the internal circulation cabinets are also included in this paper.     

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of its Brunauer–Emmett–Teller (BET) surface area. Two simulated flue gas conditions, (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, that is, more than 87%, regardless of their BET surface area.

Implications: We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had mercury adsorption efficiency comparable to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.     

苯酚的厌氧生物处理

采用不断增加苯酚浓度而降低葡萄糖浓度的方法可驯化厌氧污泥中的微生物,使厌氧污泥最终以苯酚为唯一碳源生长,可显著提高厌氧污泥降解苯酚的能力;对苯酚间歇厌氧降解过程进行了分析。苯酚浓度在0～1.680 mg/L范围内,其厌氧降解过程符合一级动力学。Aiba模型、Haldane模型和Teisser 模型均可很好地描述处于对数期时厌氧污泥的比生长速率与初始底物浓度之间的关系,其中以Teisser 模型模拟的效果最好。将驯化污泥接种于UASB中可实现对含酚废水处理的连续运行,最大的有机负荷达2 g COD/（L·d）,稳定运行时苯酚的去除率可维持在96%以上。     

A new method for the rapid determination of volatile organic compound breakthrough times for a sorbent at concentrations relevant to indoor air quality

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25%) relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Adsorption of Acid Red 73 on copper dithiocarbamate precipitate-type solid wastes

Three solid wastes, copper N,N'-bis(dithiocarboxy)piperazine ([CuBDP](n)), copper diethyldithiocarbamate (Cu(DDTC)(2)) and copper dimethyldithiocarbamate (Cu(DMTC)(2)), were prepared and tested as adsorbents to remove Acid Red 73 from wastewater. It was found that the three precipitates all could effectively adsorb the dye but their adsorption abilities were rather different. The maximum adsorption amounts of the coordination polymer precipitate [CuBDP](n) reached as high as 364mg g(-1), much greater than those of Cu(DDTC)(2) and Cu(DMTC)(2) (42.9 and 37.8mg g(-1), respectively). The investigation of adsorption models showed these adsorption processes followed the pseudo-second-order kinetic equation and the adsorption balances could be described with both Langmuir and Freundlich isotherms, but the latter seemed to be more suitable. Their adsorption nature was inferred to be physical adsorption and mainly depended on the hydrophobic interaction between these precipitates and Acid Red 73. This is the first example for the reutilization of metal dithiocarbamate precipitates as solid wastes to date.     

Bioregeneration of powdered activated carbon in the treatment of alkyl-substituted phenolic compounds in simultaneous adsorption and biodegradation processes

The role of bioregeneration process in renewing the adsorbent surface for further adsorption of organics during simultaneous adsorption and biodegradation processes has been well recognized. The extent of bioregeneration of powdered activated carbon (PAC) as an adsorbent loaded with phenol, p-methylphenol, p-ethylphenol and p-isopropylphenol, respectively, in the simultaneous adsorption and biodegradation processes were quantitatively determined using oxygen uptake as a measure of substrate consumption. Bioregeneration phenomenon was also evaluated in the simultaneous adsorption and biodegradation processes under sequencing batch reactor (SBR) operation to treat synthetic wastewater containing 1200 mg l(-1) phenol and p-methylphenol, respectively. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 4:6:1:0.75:0.25 for a cycle time of 12 h. The results show that the percentage of desorption from loaded PAC decreased in the order phenol>p-methylphenol>p-ethylphenol>p-isopropylphenol. For the treatment of phenol and p-methylphenol in the SBR reactors, respectively, the simultaneous adsorption and biodegradation processes were able to produce a consistent effluent quality of COD < or = 100 mg l(-1) when the applied PAC dosage was 0.115 and 0.143 g PAC per cycle, respectively. When no further PAC was added, the treatment performance deteriorated to that of the case without PAC addition after 68 and 48 cycles of SBR operation, respectively, for phenol and p-methylphenol. This observation is consistent with the greater extent of bioregeneration for phenol-loaded PAC as compared to p-methylphenol-loaded PAC.     

Highly effective removal of 2,4-dinitrophenolic from surface water and wastewater samples using hydrophilic molecularly imprinted polymers

Novel hydrophilic molecularly imprinted polymers (MIPs) with high adsorption capacity were used as the sorbents to remove 2,4-dinitrophenol (2,4-DNP) from surface water and wastewater samples. Kinetic studies, dynamic adsorption and selectivity experiments of hydrophilic MIPs were investigated in this study. The results indicated that the maximum adsorption capacity of 2,4-DNP on hydrophilic MIPs was 138.9 mg g^?1 and kinetic experimental data were described by the pseudo-second-order model. Furthermore, the effects of flow rate, initial concentration, pH value, and humic acid on the removal efficiency of 2,4-DNP were optimized. Compared with the active carbon, carbon nanotube, C18 sorbents and common MIPs, the removal efficiency of hydrophilic MIPs (100 mg) was very high with all above 92 % even though the sampling volume was more than 1 L. Investigated results of five times adsorption–desorption cycles indicated hydrophilic MIPs were high stability. In a word, the obtained results demonstrated that hydrophilic MIPs could be used as the effective sorbents for 2,4-DNP removal in practical application.     

Conditioning of aluminium-based water treatment sludge with Fenton's reagent: effectiveness and optimising study to improve dewaterability

Alternative conditioning of aluminium-based drinking water treatment sludge using Fenton reagent (Fe2+/H2O2) was examined in this study. Focuses were placed on effectiveness and factors to affect such novel application of Fenton process. Experiments have demonstrated that considerable improvement of alum sludge dewaterability evaluated by capillary suction time (CST) can be obtained at the relative low concentrations of Fenton reagent. A Box-Behnken experimental design based on the response surface methodology was applied to evaluate the optimum of the influencing variables, i.e. iron concentration, hydrogen peroxide concentration and pH. The optimal values for Fe2+, H2O2, and pH are 21 mg g(-1)DS(-1)(dry solids), 105 mg g(-1)DS(-1) and 6, respectively, at which the CST reduction efficiency of 48+/-3% can be achieved, this agreed with that predicted by an established polynomial model in this study.