Microwave-swing adsorption to capture and recover vapors from air streams with activated carbon fiber cloth

Adsorption with regeneration is a desirable means to control the emissions of organic vapors such as hazardous air pollutants (HAPs) and volatile organic compounds (VOCs) from air streams as it allows for capture, recovery, and reuse of those VOCs/HAPS. Integration of activated-carbon fiber-cloth (ACFC) adsorbent with microwave regeneration provides promise as a new adsorption/ regeneration technology. This research investigates the feasibility of using microwaves to regenerate ACFC as part of a process for capture and recovery of organic vapors from gas streams. A bench-scale fixed-bed microwave-swing adsorption (MSA) system was built and tested for adsorption of water vapor, methyl ethyl ketone (MEK), and tetrachloroethylene (PERC) from an airstream and then recovery of those vapors with microwave regeneration. The electromagnetic heating behavior of dry and vapor-saturated ACFC was also characterized. The MSA system successfully adsorbed organic vapors from the airstreams, allowed for rapid regeneration of the ACFC cartridge, and recovered the water and organic vapors as liquids.     

Applications of pore-expanded mesoporous silica. 7. Adsorption of volatile organic compounds

Three different varieties of mesoporous silicas were synthesized by varying the postsynthesis treatment of an as-synthesized ordered mesoporous material type MCM-41. The resulting materials consisted of a purely siliceous MCM-41, a pore-expanded MCM-41 (PE-MCM-41C), and a surfactant-laden pore-expanded MCM-41 (PE-MCM-41E) and were evaluated as adsorbents for two types of volatile organic compounds, i.e., chlorinated and aromatic hydrocarbons. Values of heat of adsorption and Henry's law constant were determined by pulse chromatography. Additionally, adsorption capacities were calculated with a dynamic method using breakthrough curves for single components in dry and humid environments. The surfactant-containing material exhibited good compatibility with chlorinated compounds in terms of heat of adsorption and efficiency in gaseous streams containing moisture. Purely siliceous mesoporous materials, i.e., MCM-41 and PE-MCM-41C, were more selective toward aromatic hydrocarbons but also gave rise to exceptionally strong adsorption.     

Mass transfer in VOC adsorption on zeolite: experimental and theoretical breakthrough curves

From experimental results of adsorption of volatile organic compounds (VOCs) on zeolite, we propose simulations of the breakthrough curves based on the Linear Driving Force model. Experiments were run on fixed beds of hydrophobic commercial zeolites. Pollutants chosen are from several chemical classes with different polarities. A good agreement between experimental and numerical results is found when an adjustable value of the internal mass-transfer coefficient is used. A constant value of effective diffusivity is found independent of the nature and the amount of VOCs adsorbed. A relation linking intrapellet mass-transfer coefficient and equilibrium constant is proposed, including the average effective diffusivity, to make predictions of breakthrough curves for any kind of volatile organic pollutant in gaseous effluents.     

Efficient removal of aromatic sulfonates from wastewater by a recyclable polymer: 2-naphthalene sulfonate as a representative pollutant

As a family of hydrophobic ionizable organic compounds, aromatic sulfonates can be present at high levels in industrial wastewaters. They tend to exist as anions over a wide range of pH and cannot be effectively trapped by conventional adsorbents. In the current study, a recyclable acrylic ester polymer (NDA-801) was synthesized for effective removal of aromatic sulfonates from wastewater of high acidity (e.g., pH < 1) and inorganic salts (e.g., approximately 5-10% Na2SO4 in mass), for which sodium 2-naphthalene sulfonate (2-NS) was chosen as a representative target contaminant 2-NS uptake onto NDA-801 increased with the increasing acidity of the solution. The zeta potential of NDA-801 measured at different pH levels as well as batch 2-NS adsorption from methanol/water binary systems demonstrated the favorable roles of electrostatic and hydrophobic interaction in 2-NS adsorption. As compared to a granular activated carbon GAC-1, NDA-801 exhibited much higher removal efficiency and capacity of 2-NS in fixed-bed adsorption. Moreover, the exhausted NDA-801 beads by 2-NS can be completely regenerated by water wash for repeated use, which is more economically desirable than by other regenerants, such as NaOH solution. Continuous column adsorption-regeneration cycles indicated negligible capacity loss of NDA-801 during operation and further validated its feasibility for potential application in associated wastewater treatment.     

Removal of formaldehyde by hydroxyapatite layer biomimetically deposited on polyamide film

Some harmful volatile organic compounds (VOCs), such as formaldehyde, are regulated atmospheric pollutants. Therefore, development of a material to remove these VOCs is required. We focused on hydroxyapatite, which had been biomimetically coated on a polyamide film, as an adsorbent and found that formaldehyde was successfully removed by this adsorbent. The amount of formaldehyde adsorbed increased with the area of the polyamide film occupied by hydroxyapatite. The amount of adsorbed formaldehyde and its rate of adsorption were larger for hydroxyapatite deposited on polyamide film than for the commercially available calcined hydroxyapatite powder. This high adsorption ability is achieved by the use of nanosized particles of hydroxyapatite with low crystallinity and containing a large number of active surface sites. Therefore, hydroxyapatite biomimetically coated on organic substrates can become a candidate material for removing harmful VOCs such as formaldehyde.     

Activated carbon fiber cloth electrothermal swing adsorption system

Capture and recovery of hazardous air pollutants (HAPs) and volatile organic compounds (VOCs) from gas streams using physical adsorption onto activated carbon fiber cloth (ACFC) is demonstrated on the bench-scale. This system is regenerated electrothermally, by passing an electric current directly through the ACFC. The adsorbate desorbs from the ACFC, rapidly condenses on the inside walls of the adsorber, and then drains from the adsorber as a pure liquid. Rapid electrothermal desorption exhibits such unique characteristics as extremely low purge gas flow rate, rapid rate of ACFC heating, rapid mass transfer kinetics inherent to ACFC, and in-vessel condensation. An existing system was scaled up 500%, and the new system was modeled using material and energy balances. Adsorption isotherms using methyl ethyl ketone (MEK) and ACFC were obtained while electricity passed through the ACFC and at temperatures above MEK's boiling point. These isotherms agreed within 7% to Dubinin-Radushkevich modeled isotherms that were extrapolated from independently determined gravimetric measurements obtained at lower temperatures. Energy and material balances for the electrothermal desorption of organic vapors and ACFC agree to within 7% of experimentally measured values. These results allow the modeling of electrothermal desorption of organic vapors from gas streams with in-vessel condensation to optimize operating conditions of the system during regeneration of the adsorbent.     

A model to predict the adsorber thermal behavior during treatment of volatile organic compounds onto wet activated carbon

A model for adsorption of volatile organic compounds (VOCs) onto a wet activated carbon bed was proposed in this study. This model accounts for temperature changes induced by the reversed and coupled mass-transfer processes of both organic species adsorption and water desorption. Indeed, it was experimentally pointed out that temperature rises, which result from the exothermal nature of the energetic interactions between the organic molecule and the activated carbon surface, are notably reduced when the adsorbent contains an initial moisture of approximately 10% in weight. Moreover, it was shown that water rate desorption was enhanced in the presence of organic vapor. This phenomenon may be explained by the displacement of sorbed water bythe organic molecules, owing to more intensive interactions with the activated carbon surface. The model proposed was elaborated from a previous comprehensive analysis of the diffusion mechanisms governing VOC adsorption at high concentrations onto a dry activated carbon bed. In a similar way, a theoretical approach was developed to model water desorption during drying of a wet activated carbon bed under pure flowing air. At last, a theoretical depiction of both competitive and reverse processes was outlined. The final model fits reasonably with experimental data relative to both breakthrough curves and thermal wave shape along the bed, even if local temperature change calculation may require some further improvement.     

现代分析测试技术在印染行业的应用(五)——气质联用技术及其在纺织工业上的应用

介绍了气相色谱一质谱联用分析技术的基本原理及其在纺织工业中的应用。气质联用分析技术可有效地用于测定纺织品中的禁用偶氮染料分解的芳香胺化合物、含氯酚类、邻苯二甲酸酯、有机锡化合物、农药残留、挥发性有机化合物等。其检测限低、灵敏度高，具有广阔的应用前景。     

Application of CSIA to distinguish between vapor intrusion and indoor sources of VOCs

At buildings with potential for vapor intrusion of volatile organic chemicals (VOCs) from the subsurface, the ability to accurately distinguish between vapor intrusion and indoor sources of VOCs is needed to support accurate and efficient vapor intrusion investigations. We have developed a method for application of compound-specific stable isotope analysis (CSIA) for this purpose that uses an adsorbent sampler to obtain sufficient sample mass from the air for analysis. Application of this method to five residences near Hill Air Force Base in Utah indicates that subsurface and indoor sources of tricholorethene and tetrachloroethene often exhibit distinct carbon and chlorine isotope ratios. The differences in isotope ratios between indoor and subsurface sources can be used to identify the source of these chemicals when they are present in indoor air.     

Improved adsorption of 4-nitrophenol onto a novel hHyper-cross-linked polymer

In the present study we prepared a hyper-cross-linked polymeric adsorbent (NDA-701) possessing a uniquely bimodal pore size distribution for 4-nitrophenol (4-NP) adsorption from water. A macroporous polymeric adsorbent Amberlite XAD-4 and a granular activated carbon GAC-1 were chosen for comparison. NDA-701 exhibited better mechanical strength and higher capacity of 4-NP than XAD-4, which possibly resulted from its hyper-cross-linking nature and micropore structure, respectively. 4-NP adsorption isotherm onto NDA-701 is well described by the Freundlich model, and its better kinetics performance than GAC-1 resulted from its macropore structure. After adsorption NDA-701 was amenable to an entire regeneration by using NaOH solution as regenerant, whereas only approximately 75% regeneration efficiency was observed for GAC-1. Results of continuous fixed-bed runs in pilot and industrial scale demonstrated that NDA-701 is capable of completely removing 4-NP from chemical effluent with no capacity loss, and 4-NP can be readily recovered by further treatment of the concentrated regenerant solution. It is attractive that the value of the recovered 4-NP from chemical wastewater will even engender a surplus after countervailing all the operation cost during field application.     

包装印刷有机废气排放控制与治理研究

从包装印刷行业有机物废气污染现状和治理重要性角度出发,结合行业有机废气排放控制标准。重点介绍了企业合理选址。有机溶剂挥发浓度控制。环保油墨应用以及高效干燥固化工艺等废气排放控制技术和热力氧化法、吸附法、等离子体氧化分解法以及膜分离法等有机废气末端治理实用技术。进而归纳总结了行业内有机废气排放控制与治理所面临的挑战。     

Sorption of trichloroethylene in hydrophobic micropores of dealuminated Y zeolites and natural minerals

Sorption of volatile organic compounds (VOCs) in low organic carbon (<0.1%) geosorbents is difficult to predict because the sorption capacity of the mineral matrix is poorly understood. This research demonstrates hydrophobic micropores can be important sorption sites for VOCs. We studied the sorption of water and TCE on three dealuminated Y zeolites ranging from hydrophilic (CBV-300) to hydrophobic (CBV-720 and CBV-780), with the surface cation density decreasing from 2.07 to 0.42 and 0.16 sites/ nm2, respectively. Water sorption and dehydration data indicate water affinity of the zeolite micropores decreases with micropore hydrophobicity. TCE sorption on the wet zeolites decreased with increasing surface cation density. At a relative pressure (P/P0) of 0.136, TCE filled only 0.034% of the micropore volume in wet CBV-300, but 16.9% and 18.6% in wet CBV-720 and CBV-780, respectively. TCE desorption data from dry and wet silica sand (Min-U-Sil 30), kaolinite (KGa-1), and smectite (SWy-1) confirmed VOC sorption in wet microporous minerals is controlled by both the micropore volume and hydrophobicity. Results suggestTCE adsorbs in hydrophobic micropores by displacing loosely bound water, consistent with the theoretical considerations indicating the process of transferring loosely bound water from hydrophobic micropores to the bulk phase is energetically favorable.     

基于GC-IMS技术分析糙米速食粥米储藏过程中风味物质的变化（网络首发、推荐阅读）

为探究糙米速食粥米储藏期间品质的变化规律,从风味化学的角度采用气相离子迁移谱技术（gas chromatography-ion mobility spectrometry,GC-IMS）,结合动态主成分分析（principal component analysis,PCA）研究糙米速食粥米储藏过程中特征挥发性有机物组成及含量的变化,并通过风味信息指纹图谱评价样品间挥发性有机物（volatile organic compounds,VOCs）的差异性。结果表明,GC-IMS联用技术可定性定量地快速鉴别不同储藏环境和储藏时间的糙米速食粥米挥发性物质的单体和二聚体,共识别59种VOCs。其中,鲜制糙米速食粥米的VOCs主要包括醛类、酮类和酯类,相对含量分别为24.44%、20.40%和43.59%。室温储藏时,随着储藏时间的延长,糙米速食粥米中醇类、醛类、吡嗪类、呋喃类含量增加,酮类、酯类含量降低;真空度对糙米速食粥米风味品质影响较小。高湿环境下,随着储藏时间的延长,有机酸类物质逐渐产生,醛类和醇类物质含量增幅较大,酮类、酯类物质减少,且随储藏温度的升高,挥发性物质变化加剧。     

Probing the adsorption characteristic of metal-organic framework MIL-101 for volatile organic compounds by quartz crystal microbalance

As volatile organic compounds (VOCs) are a major group of air pollutants, development of materials for efficient adsorption and removal of VOCs is of great significance in both environmental and analytical sciences. Here we report metal-organic frameworks (MOFs) MIL-101 for the effective adsorption of VOCs at atmospheric pressure. A simple device was designed for quartz crystal microbalance (QCM), and six VOCs with various functional groups and polarities, i.e., n-hexane, toluene, methanol, butanone, dichloromethane, and n-butylamine, were chosen as targets to probe the adsorption properties of MIL-101. The developed device allows measurement of the adsorption isotherms and monitoring of the dynamic process for the adsorption of VOCs on MOFs, and also provides a useful tool for characterization of MOFs. The adsorption isotherms of the VOCs on MIL-101 followed the Dubinin-Astakhov equation with the characteristic energy from 5.70 (methanol) to 9.13 kJ mol(-1) (n-butylamine), Astakhov exponent from 0.50 (n-butylamine) to 3.03 (n-hexane), and the limiting adsorption capacity from 0.08 (n-hexane) to 12.8 (n-butylamine) mmol g(-1). MIL-101 exhibited the strongest affinity to n-butylamine, but the weakest affinity to n-hexane. The determined Astakhov exponents and the isosteric heats of adsorption revealed the energetic heterogeneity of MIL-101. MIL-101 showed the most energetically homogeneous for n-hexane, but the most energetically heterogeneous for n-butylamine. The dynamic process of adsorption monitored by the QCM system demonstrated the distribution of the sorption sites within MIL-101. The metal sites within the MIL-101 were vital in adsorption process. MIL-101 gave much higher affinity and bigger adsorption capacity to VOCs than activated carbon, offering great potential for real applications in the adsorption and removal of VOCs.     

Evaluation of vapor intrusion using controlled building pressure

The use of measured volatile organic chemical (VOC) concentrations in indoor air to evaluate vapor intrusion is complicated by (i) indoor sources of the same VOCs and (ii) temporal variability in vapor intrusion. This study evaluated the efficacy of utilizing induced negative and positive building pressure conditions during a vapor intrusion investigation program to provide an improved understanding of the potential for vapor intrusion. Pressure control was achieved in five of six buildings where the investigation program was tested. For these five buildings, the induced pressure differences were sufficient to control the flow of soil gas through the building foundation. A comparison of VOC concentrations in indoor air measured during the negative and positive pressure test conditions was sufficient to determine whether vapor intrusion was the primary source of VOCs in indoor air at these buildings. The study results indicate that sampling under controlled building pressure can help minimize ambiguity caused by both indoor sources of VOCs and temporal variability in vapor intrusion.     

DC corona electric discharges for air pollution control. Part 1. Efficiency and products of hydrocarbon processing

A large (ca 0.7 L) wire-cylinder benchtop reactor was developed and tested for DC corona processing of VOC (volatile organic compound)-contaminated air at room temperature and pressure. The aim of our research is the identification and rationalization of the chemical reactions responsible for VOC removal. Model hydrocarbons, n-hexane and 2,2,4-trimethylpentane (i-octane), were used to characterize the process and compare the effects of DC corona polarity and of humidity on its energy efficiency and products. n-Hexane and i-octane behave very similarly. For both, the energy efficiency is significantly better with negative than with positive DC corona, especially in humid air. The effect of humidity is most interesting. Thus, while with -DC corona the process efficiency is significantly better in humid air, a slight inhibition is observed with +DC corona. Differences between +DC and -DC corona are also found in the amounts of volatile products formed, which include CO2, CO, and minor quantities of organic byproducts (aldehydes, ketones, alcohols, and lower hydrocarbons). A significant fraction of the carbon originally present as VOC is, however, unaccounted for by the analysis of gaseous and volatile organic products and must, therefore, end up as nonvolatile materials and aerosols.     

VOC sorption and diffusion behavior of building materials

In this study 25 different building materials often used in timber constructions (wood based panels, gypsum boards, vapor barriers, adhesive tapes, insulation materials and sealants) were investigated with regard to their adsorption, desorption and diffusion behaviour towards volatile organic compounds (VOC). The materials were exposed to four, respectively five selected VOCs typically found in indoor air: hexanal, butyl acetate, p-xylene, nonane and α-pinene. Adsorption and desorption properties were investigated under static conditions, whereas the diffusion behavior was examined in a 0.225 m³ emission chamber with an air exchange rate of 1 h^?1. The results of the experiments indicate that some building products have a high potential to reduce VOCs in indoor air. Apart from the vapor barriers, two insulating materials and one plasterboard, all tested materials represented an adsorption efficiency of about 50 % or higher related to the injected VOC standards. Materials with high adsorption capacity bound substances strongly and desorbed them less, whereas less adsorbing materials acted inversely. The obtained results indicate that material properties and processing play a considerable role in diffusion behavior of building materials.     

Direct measurement of VOC diffusivities in tree tissues: impacts on tree-based phytoremediation and plant contamination

Recent discoveries in the phytoremediation of volatile organic compounds (VOCs) show that vapor-phase transport into roots leads to VOC removal from the vadose zone and diffusion and volatilization out of plants is an important fate following uptake. Volatilization to the atmosphere constitutes one fundamental terminal fate processes for VOCs that have been translocated from contaminated soil or groundwater, and diffusion constitutes the mass transfer mechanism to the plant-atmosphere interface. Therefore, VOC diffusion through woody plant tissues, that is, xylem, has a direct impact on contaminant fate in numerous vegetation-VOC interactions, including the phytoremediation of soil vapors and dissolved aqueous-phase contaminants. The diffusion of VOCs through freshly excised tree tissue was directly measured for common groundwater contaminants, chlorinated compounds such as trichloroethylene, perchloroethene, and tetrachloroethane and aromatic hydrocarbons such as benzene, toluene, and methyl tert-butyl ether. All compounds tested are currently being treated at full scale with tree-based phytoremediation. Diffusivities were determined by modeling the diffusive transport data with a one-dimensional diffusive flux model, developed to mimic the experimental arrangement. Wood-water partition coefficients were also determined as needed for the model application. Diffusivities in xylem tissues were found to be inversely related to molecular weight, and values determined herein were compared to previous modeling on the basis of a tortuous diffusion path in woody tissues. The comparison validates the predictive model for the first time and allows prediction for other compounds on the basis of chemical molecular weight and specific plant properties such as water, lignin, and gas contents. This research provides new insight into phytoremediation efforts and into potential fruit contamination for fruit-bearing trees, specifically establishing diffusion rates from the transpiration stream and modeling volatilization along the transpiration path, including the trunk and branches. This work also has importance in other plant-VOC interactions, such as potential uptake from the atmosphere for hydrophobic compounds and also uptake from vapor-phase soil contaminants.     

Source apportionment of ambient volatile organic compounds in Beijing

The ambient air quality standard for ozone is frequently exceeded in Beijing in summer and autumn. Source apportionments of volatile organic compounds (VOCs), which are precursors of ground-level ozone formation, can be helpful to the further study of tropospheric ozone formation. In this study, ambient concentrations of VOCs were continuously measured with a time resolution of 30 min in August 2005 in Beijing. By using positive matrix factorization (PMF), eight sources for the selected VOC species were extracted. Gasoline-related emissions (the combination of gasoline exhaust and gas vapor), petrochemicals, and liquefied petroleum gas (LPG) contributed 52, 20, and 11%, respectively, to total ambient VOCs. VOC emissions from natural gas (5%), painting (5%), diesel vehicles (3%), and biogenic emissions (2%) were also identified. The gasoline-related, petrochemical, and biogenic sources were estimated to be the major contributors to ozone formation potentials in Beijing.     

Rapid response concentration-controlled desorption of activated carbon to dampen concentration fluctuations

Fluctuations in concentration of organic vapors in gas streams that are treated by devices such as biofilters or oxidizers make it challenging to remove the vapors from the gas streams in an efficient and economic manner. Combining adsorption with concentration-controlled desorption provides an active buffer between the source of vapors and the control device for better control of concentration and flow rate of the gas stream that is treated by the secondary control device, hence further enhancing the performance or reducing the size of the devices. Activated carbon fiber cloth is used with microwave swing adsorption to remove methyl ethyl ketone (MEK) from air streams and then provide a readily controllable feed stream of that vapor in air at a specified concentration and gas flow rate with steady-state tracking desorption. MEK was captured with >99.8% efficiency during the adsorption cycle. The MEK concentration during the regeneration cycle was readily controlled at concentration set-points between 170 and 5000 ppmv, within relative standard deviations of 1.8 and 4.9%, respectively, and at 20% of the gas flow rate that was treated during the adsorption cycle. Such capability of the system allows the secondary control device to be optimized for select constant concentrations and low gas flow rates that is not possible without such pretreatment.