Simultaneous effect of oxygen impurity and flow rate of purge gas on adsorption capacity of and heel buildup on activated carbon during cyclic adsorption-desorption of VOC.

Irreversible adsorption, or heel buildup, negatively impacts activated carbon performance and shortens its lifetime. This study elucidates the interconnections between flow rate and the oxygen impurity of desorption purge gas with heel buildup on beaded activated carbon (BAC). Nine thermal desorption scenarios were explored, varying nitrogen purge gas oxygen impurity levels (<5 ppmv, 10,000 ppmv, 210,000 ppm (21 %)) and flow rates (0.1, 1, 10 SLPM or 1 %, 10 %, 100 % of adsorption flow rate) during thermal desorption. Results reveal that increasing purge gas flow rate improves adsorption capacity recovery and mitigates adverse effects of purge gas oxygen impurity. Cumulative heel increased with higher purge gas oxygen impurity and lower flow rates. In the least effective regeneration scenario (0.1 SLPM N2, 21 % O2), a 32.8 wt% cumulative heel formed on BAC after five cycles, while the best-case scenario (10 SLPM N2, <5 ppmv O2) resulted in only 0.3 wt%. Comparing the pore size distributions of virgin and used BAC shows that heel initially forms in narrow micropores (<8.5Å) and later engages mesopores. Thermogravimetric analysis (TGA) showed that oxygen impurity creates high boiling point and/or strongly bound heel species. TGA confirmed that higher purge gas flow rates reduce heel amounts but encourage chemisorbed heel formation in oxygen's presence. These findings can guide optimization of regeneration conditions, enhancing activated carbon's long-term performance in cyclic adsorption processes.

Effect of microstructure in mesoporous adsorbents on the adsorption of low concentrations of VOCs: An experimental and simulation study.

This study evaluated the adsorption of five volatile organic compounds (VOCs) on Opoka, precipitated silica, and palygorskite, to elucidate the effect of their pore size on VOCs adsorption. The adsorption capacity of these adsorbents is not only highly correlated with their surface area and pore volume, but also notably improved by the presence of micropores. The variation in adsorption capacity for different VOCs was primarily influenced by their boiling point and polarity. Palygorskite, which had the smallest total pore volume (0.357 cm3/g) but the largest micropore volume (0.043 cm3/g) among the three adsorbents, exhibited the highest adsorption capacity for all tested VOCs. Additionally, the study constructed slit pore models of palygorskite with micropores (0.5 and 1.5 nm) and mesopores (3.0 and 6.0 nm), calculated and discussed the heat of adsorption, concentration distribution, and interaction energy of VOCs adsorbed on different pore models. The results revealed that the adsorption heat, concentration distribution, total interaction energy, and van der Waals energy decrease with increasing pore size. The concentration of VOCs in 0.5 nm pore was nearly three times that in 6.0 nm pore. This work can also provide guidance for further research on using adsorbents with mixed microporous and mesoporous structures to control VOCs.

Review of welding fume emission factor development.

The fumes created from welding activities present a unique occupational hazard. Due to the complex processes which govern fume formation, the characterization of welding fumes is difficult. Emission factors (EFs) are one method to characterize fume formation from different processes and scenarios. This paper reviews the development of EFs and similar metrics both historic research which contributed to the US EPAs AP-42 summary of welding emission factors released in 1995, and more recent research initiatives. Through a critical analysis of what research has been done in this area and the strength of the emission factors developed, this paper proposes a set of recommendations for future research. Research on emission factors for gas metal arc welding (GMAW) is the most complete amongst the different types of electric arc welding. Despite it being generally known that flux core arc welding (FCAW) creates significant fume emissions compared to some of the other processes few studies have looked at FCAW since the AP-42. Shielded metal arc welding is also under-researched particularly in terms of metal-specific emission factors. The influence of different welding activity parameters such as welding location, speed or current is well defined for GMAW but requires more attention for other welding processes. Further effort towards compiling and comparing available emission factor data of quality, evaluating the available data statistically and organizing this data in a practically useful way is required. The availability of reliable emission factors will allow the development or improvement of exposure modelling tools that would be very useful for exposure assessment when monitoring is not practical.s.

Prediction of heel build-up on activated carbon using machine learning.

Determining the long-term performance of adsorbents is crucial for the design of air treatment systems. Heel buildup i.e., the accumulation of non-desorbed/ non-desorbable adsorbates and their reaction byproducts, on the surface/pores of the adsorbent is a primary cause of adsorption performance deterioration. However, due to the complexity of heel buildup mechanisms, theoretical models have yet to be developed to map the extent of heel buildup to the adsorption/desorption parameters. In this work, two machine learning (ML) algorithms (XGBoost and neural network (NN)) were applied to predict volatile organic compounds (VOCs) cyclic heel buildup on activated carbons (ACs) by considering the adsorbent characteristics, adsorbate properties and regeneration conditions. The NN algorithm showed better performance in prediction of cyclic heel buildup (R2 = 0.94) than XGBoost (R2 = 0.81). To analyze interaction between heel buildup and adsorbent characteristics, adsorbate properties, and regeneration conditions, partial dependency plots were generated. The proposed ML-based heel prediction methods can be ultimately used to: (i) optimize adsorption/desorption operating conditions to minimize heel buildup on activated carbon in cyclic adsorption/desorption processes and (ii) quickly screen various adsorbents for efficient adsorption/desorption of a particular family of VOCs by excluding adsorbents prone to high heel formation.

Graphene oxide enhances thermal stability and microwave absorption/regeneration of a porous polymer.

Microwave regeneration of adsorbents offers several advantages over conventional regeneration methods; however, its application for microwave transparent adsorbents such as polymers is challenging. In this study, hypercrosslinked polymer/graphene oxide (GO) nanocomposites with large surface area and enhanced microwave absorption ability were synthesized. Polymers of 4, 4´-bis ((chloromethyl)-1, 1´-biphenyl- benzyl chloride) were hypercrosslinked through the Friedel-Crafts reactions. GO sheets were synthesized through the Hummer's method. Nanocomposites with different GO contents (1-8 wt%) were synthesized by solution mixing method. Thermogravimetry analysis revealed a large enhancement in the thermal stability of GO-filled nanocomposites compared to pristine polymer. N2 adsorption isotherm analysis showed 7% and 10% reduction in BET surface area and total pore volume of the nanocomposite with 8 wt% GO. Compared to the pristine polymer, the dielectric constant and dielectric loss factor increased from 5 to 17 and 0.05-1.6, respectively, for the nanocomposites with 8 wt% GO. Microwave-assisted desorption of toluene from samples revealed more than 160 ºC and 4 times improvement in the desorption temperature and desorption efficiency, respectively, by addition of 4 wt% GO to the polymer. This study showed the important role of GO addition for efficient microwave-assisted regeneration of polymer adsorbents.

Porous carbon black-polymer composites for volatile organic compound adsorption and efficient microwave-assisted desorption.

Adsorbents with high surface area, thermal stability and microwave absorption ability are highly desired for cyclic adsorption and microwave regeneration processes. However, most polymeric adsorbents are transparent to microwaves. Herein, porous hyper-crosslinked polymers (HCP) of (4,4'-bis((chloromethyl)-1,1'-biphenyl-benzyl chloride)) with different carbon black (CB) contents were synthesized via the Friedel-Crafts reaction. CB was selected as the filler due to its low cost and high dielectric loss and was embedded inside the polymer structure during polymerization. CB-containing composites showed enhanced thermal stability at elevated temperatures, and more than a 90-times increase in the dielectric loss factor, which is favorable for microwave regeneration. Nitrogen physisorption analysis by the Bruner-Emmett-Teller isotherms demonstrated that CB presence in the polymer structure nonlinearly decreases the surface area and total pore volume (by 38% and 26%, respectively at the highest CB load). Based on the characterization testing, 4 wt% of CB was found to be an optimum filler content, having the highest MW absorption and minimal effect on the adsorbent porosity. HCP with 4 wt% CB allowed a substantial increase in the desorption temperature and yielded more than a 450% enhancement in the desorption efficiency compared to HCP without CB.

Mathematical correlations in two-phase modeling of fluidized bed adsorbers.

Choosing proper formulas for estimating different variables is imperative when modeling a fluidized bed using two-phase theory. In this study, a two-phase model was used to model the adsorption of volatile organic compounds (VOC) in a multistage fluidized bed adsorber. Two different approaches were used to describe gas flow and mixing in the emulsion phase, perfectly mixed (EGPM: Emulsion Gas - Perfectly Mixed) and plug flow (EGPF: Emulsion Gas - Plug flow). The impact of different formulas for estimating bubble size, bed porosity at minimum fluidization velocity, adsorption and interphase mass transfer coefficients, as well as tortuosity on the performance of the model was determined by comparing the model outcomes with experimental data. Finally, using a large dataset obtained from fluidized bed adsorption systems with different adsorbents, adsorbates, bed sizes, and operating conditions, a broadly-applicable set of formulas was suggested which could be used to describe the behavior of different countercurrent fluidized bed adsorbers. From the results, the two-phase model could successfully predict the experimental data, with EGPF showing better performance than EGPM. Proper use of formulas, especially those describing bed voidage and interphase mass transfer coefficient, could markedly improve the performance of the two-phase model. The two-phase model using the set of formulas proposed here was able to accurately replicate a large dataset of fluidized bed adsorption experiments over a wide range of operating conditions.

Mesoporous MCM-41 derived from natural Opoka and its application for organic vapors removal.

Mesoporous silica MCM-41 was synthesized by a facile hydrothermal treatment using sodium silicate extracted from natural Opoka as the Si source. The dynamic adsorption and desorption of organic vapors mixture on the MCM-41 were investigated. Characterization of the textural properties of the samples showed that the sample synthesized with a molar ratio of CTAB/Si = 0.16 possessed the largest specific surface area (988 m2/g) and pore volume (1.02 cm3/g), also uniform pore size distribution centered at 2.8 nm. The adsorption capacity of this sample for organic vapors mixture improved remarkably over raw Opoka and reached 158.5 mg/g at 20 â„ƒ, which is comparable to that of commercial activated carbon. The reusability of the adsorbent was tested by 5 adsorption and regeneration cycles. Obtained results demonstrate that the MCM-41 adsorbent can be easily regenerated by thermal desorption in air, and the cumulative heel on the adsorbent can be markedly reduced by increasing the desorption temperature, making it a promising adsorbent for VOCs abatement.

Modeling VOC adsorption in lab- and industrial-scale fluidized bed adsorbers: Effect of operating parameters and heel build-up.

Scale-up and optimization of fluidized beds are challenging due to the difficulty in accounting for the interrelated effect of various phenomena, which are typically described by empirical and/or semi-empirical equations. In this study, a two-phase model was introduced to simulate the adsorption of VOCs on beaded activated carbon (BAC) in a lab-scale fluidized bed adsorber. The model assumes the presence of a bubble phase free from adsorbent particles, and an emulsion phase composed of the adsorbent particles and interstitial gas. The versatility of the proposed model was then evaluated using data from an industrial scale adsorber with different operating conditions, adsorbent properties, and bed geometry. The response of the model to the operating conditions (adsorbent feed rate, air flow rate and initial concentration) showed better agreement with the experimental lab-scale data when the emulsion gas in two-phase model was considered in plug flow than in perfectly-mixed flow (R2 = 0.96 compared to 0.91). To simulate the performance of BACs with different service lifetimes (degree of exhaustion as a result of heel developed inside their pores), the main characteristics of the BACs (pore diameter, porosity, and adsorption capacity) were first correlated to their apparent densities. The model could accurately predict the experimental lab-scale VOC concentrations in each stage (R2 = 0.92) as well as overall removal efficiencies (R2 = 0.99) for BACs ranging from virgin to fully-spent. Finally, the model was used to predict the performance of an industrial-scale fluidized bed adsorber for VOC removal at different operating conditions and apparent densities. Predicted and measured VOC removal efficiencies were in good agreement (R2 = 0.94). Although the model was verified for adsorption of VOCs on BAC, the modeling approach presented in this study could be used for describing adsorption in different adsorbate-adsorbent systems in multistage counter-current fluidized bed adsorbers.

Modeling the Effect of Relative Humidity on Adsorption Dynamics of Volatile Organic Compound onto Activated Carbon.

A two-dimensional heterogeneous mathematical model was developed and validated to study the effect of relative humidity on volatile organic compound (VOC) adsorption onto activated carbon. The dynamic adsorption model consists of the macroscopic mass, momentum, and energy conservation equations and includes a multicomponent adsorption isotherm to predict the competitive adsorption equilibria between VOC and water vapor, which is described by an extended Manes method. Experimental verifications show that the model predicted the breakthrough profiles during competitive adsorption of the studied VOCs (2-propanol, acetone, n-butanol, toluene, 1,2,4-trimethylbenzene) at relative humidity range 0-95% with an overall mean relative absolute error (MRAE) of 11.8% for dry (0% RH) conditions and 17.2% for humid (55 and 95% RH) conditions, and normalized root-mean-square error (NRMSE) of 5.5 and 8.4% for dry and humid conditions, respectively. Sensitivity analysis was also conducted to test the robustness of the model in accounting for the impact of relative humidity on VOC adsorption by varying the adsorption temperature. Good agreement was observed between the experimental and simulated results with an overall MRAE of 12.4 and 7.1% for the breakthrough profiles and adsorption capacity, respectively. The model can be used to quantify the impact of carrier gas relative humidity during adsorption of contaminants from gas streams, which is useful when optimizing adsorber design and operating conditions.

Adsorption of volatile organic compounds onto natural porous minerals.

The abundance of natural porous minerals and their low cost make them the potential adsorbents for VOCs (volatile organic compounds). In this paper, three natural minerals (diatomite, stellerite and vitric tuff) and their corresponding acid-treated minerals were used as adsorbents. The adsorption performances of minerals were investigated by the adsorption breakthrough curves of VOCs. The results indicated that the properties of organic compounds such as boiling point and polarity and the surface area and pore volume of minerals had obvious effects on the adsorption of VOCs over minerals. Increasing adsorption temperature and relative humidity would have negative effects on the VOC adsorption of minerals. The adsorption capacity of 2-heptanone over acid stellerite decreased by 7.2% as the temperature rose from 25°C to 45°C. The adsorption capacity of acid stellerite for 2-heptanone reduced by 60.9% when relative humidity increased from 0% to 75%. Minerals were tested for five adsorption-regeneration cycles to study the reusability. Better fittings of Thomas model, pseudo-first order kinetics model, and Freundlich model were showed in fitting the adsorption. Overall, porous minerals with high specific surface area and pore volume have promising prospect in VOCs adsorption.

Effect of naphtha diluent on greenhouse gases and reduced sulfur compounds emissions from oil sands tailings.

The long-term storage of oil sands tailings has resulted in the evolution of greenhouse gases (CH4 and CO2) as a result of residual organics biodegradation. Recent studies have identified black, sulfidic zones below the tailings-water interface, which may be producing toxic sulfur-containing gases. An anaerobic mesocosm study was conducted over an 11-week period to characterize the evolution of CH4, CO2 and reduced sulfur compounds (RSCs) (including H2S) in tailings as it relates to naphtha-containing diluent concentrations (0.2, 0.8, and 1.5% w/v) and microbial activity. Our results showed that RSCs were produced first at 0.12µmol°RSCs/mL MFT (1.5% w/v diluent treatment). RSCs contribution (from highest to lowest) was H2S and 2-methylthiophene>2.5-dimethylthiophene>3-methylthiophene>thiofuran>butyl mercaptan>carbonyl sulfide, where H2S and 2-methylthiophene contributed 81% of the gas produced. CH4 and CO2 production occurred after week 5 at 40.7µmolCH4/mL MFT and 5.9µmolCO2/mL MFT (1.5% w/v diluent treatment). The amount of H2S and CH4 generated is correlated to the amount of diluent present and to microbial activity as shown by corresponding increases in sulfate-reducers' Dissimilatory sulfite reductase (DsrAB) gene and methanogens' methyl-coenzyme M reductase (MCR) gene.

Autonomous mobile platform for monitoring air emissions from industrial and municipal wastewater ponds.

Significant amounts of volatile organic compounds and greenhouse gases are generated from wastewater lagoons and tailings ponds in Alberta, Canada. Accurate measurements of these air pollutants and greenhouse gases are needed to support management and regulatory decisions. A mobile platform was developed to measure air emissions from tailings pond in the oil sands region of Alberta. The mobile platform was tested in 2015 in a municipal wastewater treatment lagoon. With a flux chamber and a CO2/CH4 sensor on board, the mobile platform was able to measure CO2 and CH4 emissions over two days at two different locations in the pond. Flux emission rates of CO2 and CH4 that were measured over the study period suggest the presence of aerobic and anaerobic zones in the wastewater treatment lagoon. The study demonstrated the capabilities of the mobile platform in measuring fugitive air emissions and identified the potential for the applications in air and water quality monitoring programs. IMPLICATIONS: The Mobile Platform demonstrated in this study has the ability to measure greenhouse gas (GHG) emissions from fugitive sources such as municipal wastewater lagoons. This technology can be used to measure emission fluxes from tailings ponds with better detection of spatial and temporal variations of fugitive emissions. Additional air and water sampling equipment could be added to the mobile platform for a broad range of air and water quality studies in the oil sands region of Alberta.

A Novel Technique for Determining the Adsorption Capacity and Breakthrough Time of Adsorbents Using a Noncontact High-Resolution Microwave Resonator Sensor.

A newly developed noncontact high-resolution real-time microwave sensor was used to determine the breakthrough time and adsorption capacity of adsorbents/adsorbates with different dielectric properties. The sensor is a microwave microstrip planar resonator with an enhanced quality factor using a regenerative feedback loop operating at 1.4 GHz and an adjustable quality factor of 200-200000. Beaded activated carbon (BAC, microwave-absorbing) and a polymeric adsorbent (V503, microwave transparent) were completely loaded with 1,2,4-trimethylbenzene (nonpolar) or 2-butoxyethanol (polar). During adsorption, variations in the dielectric properties of the adsorbents were monitored using two microwave parameters; quality factor and resonant frequency. Those parameters were related to adsorption breakthrough time and capacity. Adsorption tests were completed at select relative pressures (0.03, 0.1, 0.2, 0.4, and 0.6) of adsorbates in the influent stream. For all experiments, the difference between the breakthrough time (t5%) and the settling time of the quality factor variation (time that the quality factor was 0.95 of its final value) was <5%. Additionally, a linear relationship between the final value of the resonant frequency shift and adsorption capacity was observed. The proposed noncontact sensor can be used to determine the breakthrough time and adsorption capacity.

The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials.

The role of beaded activated carbon's pore size distribution on heel formation during cyclic adsorption/desorption of organic vapors.

The effect of activated carbon's pore size distribution (PSD) on heel formation during adsorption of organic vapors was investigated. Five commercially available beaded activated carbons (BAC) with varying PSDs (30-88% microporous) were investigated. Virgin samples had similar elemental compositions but different PSDs, which allowed for isolating the contribution of carbon's microporosity to heel formation. Heel formation was linearly correlated (R(2)=0.91) with BAC micropore volume; heel for the BAC with the lowest micropore volume was 20% lower than the BAC with the highest micropore volume. Meanwhile, first cycle adsorption capacities and breakthrough times correlated linearly (R(2)=0.87 and 0.93, respectively) with BAC total pore volume. Micropore volume reduction for all BACs confirmed that heel accumulation takes place in the highest energy pores. Overall, these results show that a greater portion of adsorbed species are converted into heel on highly microporous adsorbents due to higher share of high energy adsorption sites in their structure. This differs from mesoporous adsorbents (low microporosity) in which large pores contribute to adsorption but not to heel formation, resulting in longer adsorbent lifetime. Thus, activated carbon with high adsorption capacity and high mesopore fraction is particularly desirable for organic vapor application involving extended adsorption/regeneration cycling.

Automotive Wastes.

A review of the literature from 2014 related to automotive wastes is presented. Topics include solid wastes from autobodies and tires as well as vehicle emissions to soil and air as a result of the use of conventional and alternative fuels. Potential toxicological and health risks related to automotive wastes are also discussed.

Using microwave heating to improve the desorption efficiency of high molecular weight VOC from beaded activated carbon.

Incomplete regeneration of activated carbon loaded with organic compounds results in heel build-up that reduces the useful life of the adsorbent. In this study, microwave heating was tested as a regeneration method for beaded activated carbon (BAC) loaded with n-dodecane, a high molecular weight volatile organic compound. Energy consumption and desorption efficiency for microwave-heating regeneration were compared with conductive-heating regeneration. The minimum energy needed to completely regenerate the adsorbent (100% desorption efficiency) using microwave regeneration was 6% of that needed with conductive heating regeneration, owing to more rapid heating rates and lower heat loss. Analyses of adsorbent pore size distribution and surface chemistry confirmed that neither heating method altered the physical/chemical properties of the BAC. Additionally, gas chromatography (with flame ionization detector) confirmed that neither regeneration method detectably altered the adsorbate composition during desorption. By demonstrating improvements in energy consumption and desorption efficiency and showing stable adsorbate and adsorbent properties, this paper suggests that microwave heating is an attractive method for activated carbon regeneration particularly when high-affinity VOC adsorbates are present.