A comparative study on the performance of M (Rh,Ru, Ni)-promoted metallurgical waste driven catalysts for H2 production by glycerol steam reforming

A comprehensive study was conducted on the performance of M-promoted (M = 1%Ru, 1%Rh, 5%Ni) upgraded slag oxide metallurgical waste catalysts (M-UGSO) for hydrogen production by glycerol steam reforming (GSR). The results confirmed that the tendency of the incorporated metal to interact with Mg/Fe containing species within UGSO plays a key role in the surface availability of the corresponding metal, structural changes after reduction, and catalyst stability. Aside its best stability, 5% Ni-UGSO showed a performance (glycerol conversion to gaseous products of 100% and H₂ yield of 74%) comparable with 1% Rh-UGSO (100% and 78%, respectively) or even surpassing that of 1% Ru-UGSO (94% and 71%, respectively), as noble metal-based catalysts. Synergistic cooperation was achieved by incorporated metals (M) and Fe/Mg containing species within UGSO, resulting in enhanced glycerol and water activation. The weakest results of Ru-UGSO could be justified by lack of propensity for MgO–RuO₂ interaction on UGSO surface.     

Use of micellar extraction and cloud point preconcentration for valorization of saponins from sisal (Agave sisalana) waste

Sisal (Agave sisalana) is the main hard fiber produced worldwide, with an estimated generation of 400 thousands t in 2011. From its leaves, only the hard fibers, which represent 3–5% of their weight, are removed. The remaining 95–97% is referred to as sisal waste and contains steroidal saponins that can be potentially used in foods, cosmetics and pharmaceuticals formulations, as well as for soil bioremediation. The present work aimed at to evaluate strategies for the extraction and concentration of saponins from sisal waste, focused on the use of clean solvents, such as water and ethanol. For this purpose, it was firstly performed a central composite rotatable design for the optimization of the extraction conditions followed by a comparison of this strategy with other methods (Soxhlet, ultrasound-assisted extraction and micellar extraction). Cloud point preconcentration was then tested, using several types and concentrations of salts. The use of orbital shaker extraction (200 rpm) with an ethanolic solution (30%, v/v) at 50 °C, a mass/volume ratio sisal/solvent of 0.17 (g/mL) for 4 h allowed a recovery of 38.6% of the saponins. When a micellar extraction strategy using 7.5% (v/v) of Triton X-100, under the above-mentioned conditions was performed, saponins recovery raised to 98.4%. In a subsequent step, the addition of 20% (m/v) sodium carbonate led to a preconcentration factor of 20.3. The best adsorbent for Triton removal from the preconcentrated solution was Amberlite FPX-66. The process strategy proposed in the present study showed to be efficient for saponins extraction and preconcentration from a low-cost, highly available agricultural waste.     

Assessing anodic microbial populations and membrane ageing in a pilot microbial electrolysis cell

First large-scale experiences of bioelectrochemical systems (BES) are underway. However, there is still little knowledge on how the different elements that integrate a BES behave in near real-life conditions. This paper aims at assessing the impact of long-term operation on the cation exchange membrane and on the anodic biofilm of two 16 L Microbial Electrolysis Cells (MEC) designed for hydrogen production and ammonia recovery from pig slurry. Membrane deterioration was examined by physical, chemical and microscopy techniques at different locations, revealing a strong attachment of microorganisms and a significant decay in membrane properties such as ion exchange capacity and thermal stability. Anode microbial communities did not show a dramatic shift in the eubacteria composition at different sampling areas, although the relative abundance of some bacterial groups showed a clear vertical stratification. After 100 days of continuous operation, MEC performance did not declined significantly maintaining ammonium transport rates and H₂ production rates of 15.3 gN d⁻¹ m⁻² and 0.2 LH₂·L⁻¹_reactor·d⁻¹ respectively.     

Strategies of valorization of sludge from wastewater treatment

Sludge is regarded as a potential source to achieve valorization via strategies such as resource recovery, sludge based adsorbents preparation, bioflucculants production, sludge manufacturing construction materials preparation, sludge composting and thermal valorization, which are currently common and effective strategies. Appropriate treatment strategies of sludge are of great importance worldwide for the fast growing population and rapidly increasing waste. This mini review summarized some widely used and effective strategies to achieve sludge valorization based on whether the strategy would utilize or reuse the potential of sludge to obtain valuable product and eliminate secondary pollution. Anaerobic digestion of sludge is perceived as a potentially cost‐effective method to achieve sludge reduction and resource recovery including carbon, nitrogen, phosphorus resource recovery coupled with other technologies. Utilizing sludge as raw material for preparation of valuable products including sludge based adsorbents, bioflocculants and construction materials is another aspect to achieve sludge valorization. Sludge composting and thermal valorization are also introduced in the mini review since the two strategies could also achieve sludge valorization. In addition, the strategies mentioned were discussed and analyzed in the mini review from environmental and economic aspects. © 2017 Society of Chemical Industry     

Microstructural development and electrical behavior during crystalization of iron-rich glass-ceramics obtained from mill scale

Mill scale is one of the most hazardous waste generated from the steelmaking industry. In 2014, around 16.4–32.8 million t of mill scale was generated all over the world. In this paper, we present recent results about the effect of the structure and microstructure of iron-rich glass-ceramics obtained from mill scale on their electrical behavior. Five iron-rich glass compositions were investigated. The crystalline phases of the crystallized (glass-ceramic) materials were identified by X-ray diffractometry, and phase content quantifications were performed by the Rietveld method. The crystallinity and porosity were also related to the electrical behavior of the glass-ceramics, which was determined by impedance spectroscopy, and the hardness, measured by the Vickers indentation method. Albite, andradite, anorthite, clinopyroxene, franklinite, nepheline, and spinel were shown to be the main crystalline phases present in the investigated compositions. The conductivity showed an increasing trend with the degree of crystallinity. This behavior was attributed to a decrease in porosity, an increase in the concentration of charge carriers in the glass phase (iron, Li⁺, and Na⁺), and an increase in the number of conduction paths through the glassy phase/crystalline phase interfaces. The relationship between hardness and crystallinity could not be verified due to the structural complexity of the glass-ceramics studied. However, a nearly linear relationship was found between the effect of porosity and hardness. The G2Z composition exhibited a hardness of 6.1 ± 0.5 GPa at 850 °C, which is a value in very good agreement with other iron-rich glass-ceramics studied.     

Role of lignin in a biorefinery: separation characterization and valorization

Lignin, a major component of the cell wall of vascular plants, has long been recognized for its negative impact and treated as a by‐product in a biorefinery. This highly abundant by‐product of the biorefinery is undervalued and underdeveloped due to its complex nature. The development of value‐added products from lignin would greatly improve the economics of the biorefinery. The inherent properties of lignin significantly affect the productivity of the biorefinery processes and its potential applications. Although the structure and biosynthetic pathway of lignin have been studied for more than a century, they have not yet been completely elucidated. In this mini‐review, the primary obstacles to elucidating the structure of native lignin, including separation and characterization, are highlighted. Several classical methods for separation and various NMR techniques, especially 2D HSQC NMR, for characterization of lignin are reviewed. Some potential applications of lignin are introduced. It is believed that a knowledge of the method to separate lignin from the cell wall and structural features of the lignin polymer from lignocellulosic materials will help to maximize the exploitation of lignocelluloses for the biorefinery as well as the utilization of lignin for novel materials and chemicals. © 2012 Society of Chemical Industry