Biophotocatalytic Reduction of CO2 in Anaerobic Biogas Produced from Wastewater Treatment Using an Integrated System

This study presents the bio-photocatalytic upgrading of biogas utilising carbon dioxide (CO2) as a potential option for beginning fossil fuel depletion and the associated environmental risks in the pursuit of sustainable development. Herein, magnetite photocatalyst (Fe-TiO2) was employed with an integrated anaerobic-photomagnetic system for the decontamination of municipality wastewater for biogas production. The Fe-TiO2 photocatalyst used, manufactured via a co-precipitation technique, had a specific surface area of 62.73 m2/g, micropore volume of 0.017 cm3/g and pore size of 1.337 nm. The results showed that using the ultraviolet-visible (UV-Vis) photomagnetic system as a post-treatment to the anaerobic digestion (AD) process was very effective with over 85% reduction in colour, chemical oxygen demand (COD) and turbidity. With an organic loading rate (OLR) of 0.394 kg COD/L·d and hydraulic retention time (HTR) of 21 days, a 92% degradation of the organic content (1.64 kgCOD/L) was attained. This maximised the bioenergy production to 5.52 kWh/m3 with over 10% excess energy to offset the energy demand of the UV-Vis lamp. Assuming 33% of the bioenergy produced was used as electricity to power the UV-Vis lamp, the CO2 emission reduction was 1.74 kg CO2 e/m3, with good potential for environmental conservation.

Photocatalytic Performance of Carbon-Containing CuMo-Based Catalysts under Sunlight Illumination

Carbon-doped nanostructured CuMo-based photocatalysts were prepared by solvothermal synthesis. Two thermal treatments—oxidative and inert atmosphere—were used for the synthesis of the catalysts, and the influence of spherical carbon structures upon the crystalline phases on the photocatalytic activity and stability was studied. XRD showed the catalysts are nanostructured and composed by a mixture of copper (Cu, Cu2O, and CuO) and molybdenum (MoO2 and MoO3) crystalline phases. The catalysts were used for the degradation of yellow 5 under solar light. A remarkable leaching of Mo both in dark and under solar irradiation was observed and quantified. This phenomenon was responsible for the loss of photocatalytic activity for the degradation of the dye on the Mo-containing series. Conversely, the Cu-based photocatalysts were stable, with no leaching observed after 6 h irradiation and with a higher conversion of yellow 5 compared with the Mo- and CuMo series. The stability of Cu-based catalysts was attributed to a protective effect of spherical carbon structures formed during the solvothermal synthesis. Regarding the catalysts’ composition, sample Cu4-800-N2 prepared by pyrolysis exhibited up to 4.4 times higher photoactivity than that of the pristine material, which is attributed to a combined effect of an enhanced surface area and micropore volume generated during the pyrolytic treatment due to the presence of the carbon component in the catalyst. Scavenger tests have revealed that the mechanism for tartrazine degradation on irradiated Cu-based catalysts involves successive attacks of •OH radicals.

Microporous Volumes from Nitrogen Adsorption at 77 K: When to Use a Different Standard Isotherm?

This work reviews the application of various standard isotherms to evaluate the micropore volume in a range of microporous materials. The selected materials have quite different surface chemistry, and are relevant due to their properties for adsorption and catalysis: zeolites, activated carbons, clay-based materials and MOFs. Some cases were analysed before and after being used as supports in the heterogenization of homogeneous catalysts. The discussion is centred, but not limited, to the three standard isotherms that are mostly employed in the literature (t-curve, non-porous carbon and non-porous hydroxylated silica) for the assessment of the micropore volume. For a given material the values of the micropore volumes from the different standard isotherms were compared, particularly against the values from the largely used t-curve. The cases where major discrepancies were found could normally be ascribed to samples that have a broad micropore size distribution.

Changes in Porous Parameters of the Ion Exchanged X Zeolite and Their Effect on CO2 Adsorption

Zeolite 13X (NaX) was modified through ion-exchange with alkali and alkaline earth metal cations. The degree of ion exchange was thoroughly characterized with ICP, EDS and XRF methods. The new method of EDS data evaluation for zeolites was presented. It delivers the same reliable results as more complicated, expensive, time consuming and hazardous ICP approach. The highest adsorption capacities at 273 K and 0.95 bar were achieved for materials containing the alkali metals in the following order K < Na < Li, respectively, 4.54, 5.55 and 5.94 mmol/g. It was found that it is associated with the porous parameters of the ion-exchanged samples. The Li0.61Na0.39X form of zeolite exhibited the highest specific surface area of 624 m2/g and micropore volume of 0.35 cm3/g compared to sodium form 569 m2/g and 0.30 cm3/g, respectively. The increase of CO2 uptake is not related with deterioration of CO2 selectivity. At room temperature, the CO2 vs. N2 selectivity remains at a very high stable level prior and after ion exchange in co-adsorption process (XCO2 during adsorption 0.15; XCO2 during desorption 0.95) within measurement uncertainty. Additionally, the Li0.61Na0.39X sample was proven to be stable in the aging adsorption-desorption tests (200 sorption-desorption cycles; circa 11 days of continuous process) exhibiting the CO2 uptake decrease of about 6%. The exchange with alkaline earth metals (Mg, Ca) led to a significant decrease of SSA and micropore volume which correlated with lower CO2 adsorption capacities. Interestingly, the divalent cations cause formation of mesopores, due to the relaxation of lattice strains.

Research on Powdered Activated Carbon Modification Using Chosen Chemical Methods

Activated carbon has many applications in the environment, cosmetology, medicine and industry. The surface of each activated carbon can be modified to obtain the desired adsorption properties. Chemical activation can greatly affect the adsorption efficiency, control activity and application of the activated carbon. The aim of the study was to modify the selected activated carbon by chemical and physical methods, while maintaining these parameters so that it could be used in medicine. Powdered activated carbons with higher mechanical strength, large specific surface area and large macro-, meso- and micropore volume were prepared using natural waste wood material. This was followed by the digestion process and the washing of activated carbon. The study results indicate a significant influence of the centrifugal washing of activated carbon on the changes in the ash content and methylene index in the final product.

The Characteristics and Main Controlling Factors for the Formation of Micropores in Shale from the Niutitang Formation, Wenshuicun Section, Southwest China

The characteristics of shale micro-pore development and its main influencing factors have important theoretical guiding significance for shale gas exploration and resource evaluation. In order to clarify the micro-pore development characteristics of lower Cambrian shale and the main controlling factors of micro-pore development, we used the lower Cambrian Niutitang formation shale, in the Wenshuicun section of the Guizhou Province in southwest China. The micro-pore development characteristics of the shale in the region were studied by argon ion profile field emission scanning electron microscopy and a low-temperature liquid nitrogen adsorption and desorption experimental system. The relationship between micro-pore and kerogen maceral composition, total organic carbon (TOC) content and different mineral content was analyzed in combination with mineral and geochemical characteristics. Inorganic pores (clay mineral pores, dissolution pores and pyrite intergranular pores) and micro-fractures (clay mineral shrinkage crack, tectonic fractures and overpressure fractures) were the main type of pore developed in the shale of the Niutitang formation in the Wenshuicun section, and no organic pores had developed. The pore size of shale is usually 2–50 nm, accounting for 58.33% of shale pores, e.g. mesopores. Clay mineral content has an obvious positive correlation with macropore volume and average pore diameter, and an obvious negative correlation with micropore volume. In addition, the content of feldspar in brittle minerals has a strong negative correlation with macropore volume and average pore diameter, and a strong positive correlation with micropore volume and BET-specific surface area. TOC content and the content of different kerogen macerals have no obvious correlation with the development of shale micropores in this region. It is concluded that inorganic mineral composition is the main controlling factor of micro-pore development within lower Cambrian shale, and organic matter abundance and maceral content have little influence on the micro-pore development. This study provides a case study for the characteristics of micropores in lower Cambrian shale in China.

Activated Carbon from Palm Date Seeds for CO2 Capture

The process of carbon dioxide capture and storage is seen as a critical strategy to mitigate the so-called greenhouse effect and the planetary climate changes associated with it. In this study, we investigated the CO2 adsorption capacity of various microporous carbon materials originating from palm date seeds (PDS) using green chemistry synthesis. The PDS was used as a precursor for the hydrochar and activated carbon (AC). Typically, by using the hydrothermal carbonization (HTC) process, we obtained a powder that was then subjected to an activation step using KOH, H3PO4 or CO2, thereby producing the activated HTC-PDS samples. Beyond their morphological and textural characteristics, we investigated the chemical composition and lattice ordering. Most PDS-derived powders have a high surface area (>1000 m2 g−1) and large micropore volume (>0.5 cm3 g−1). However, the defining characteristic for the maximal CO2 uptake (5.44 mmol g−1, by one of the alkaline activated samples) was the lattice restructuring that occurred. This work highlights the need to conduct structural and elemental analysis of carbon powders used as gas adsorbents and activated with chemicals that can produce graphite intercalation compounds.

Enhanced Removal of Pb from Electrolytic Manganese Anode Slime by Vacuum Carbothermal Reduction

Electrolytic manganese anode slime (EMAS) is produced during the production of electrolytic manganese metal. In this study, a method based on vacuum carbothermal reduction was used for Pb removal in EMAS. A Pb-removal efficiency of 99.85% and MnO purity in EMAS of 97.34 wt.% was obtained for a reduction temperature of 950°C and a carbon mass ratio of 10% for a holding time of 100 min. The dense structure of the EMAS was destroyed, a large number of multidimensional pores and cracks were formed, and the Pd-containing compound was reduced to elemental Pb by the vacuum carbothermal reduction. A recovery efficiency for chemical MnO2 of 36.6% was obtained via preparation from Pd-removed EMAS through the “roasting-pickling disproportionation” process, with an acid washing time of 100 min, acid washing temperature of 70°C, H2SO4 concentration of 0.8 mol/L, liquid-solid mass ratio of 7 mL/g, calcination temperature of 60°C and calcination time of 2.5 h. Moreover, the crystal form of the prepared chemical MnO2 was found to be basically the same as that of electrolytic MnO2, and its specific surface area, micropore volume and discharge capacity were all higher than that of electrolytic MnO2. This study provides a new method for Pd removal and recycling for EMAS.