Sugarcane is the most produced agricultural commodity in tropical and subtropical regions, where it is primarily used for the production of sugar and ethanol. The latter is mostly used to produce alcoholic beverages as well as low carbon biofuel. Despite well-established production chains, their respective residues and by-products present unexploited potentials for further product portfolio diversification. These fully or partially untapped product streams are a) sugarcane trash or straw that usually remain on the fields after mechanized harvest, b) ashes derived from bagasse combustion in cogeneration plants, c) filter cake from clarification of the sugarcane juice, d) vinasse which is the liquid residue after distillation of ethanol, and e) biogenic CO2 emitted during bagasse combustion and ethanol fermentation. The development of innovative cascading processes using these residual biomass fractions could significantly reduce final disposal costs, improve the energy output, reduce greenhouse gas emissions, and extend the product portfolio of sugarcane mills. This study reviews not only the state-of-the-art sugarcane biorefinery concepts, but also proposes innovative ways for further valorizing residual biomass. This study is therefore structured in four main areas, namely: i) Cascading use of organic residues for carboxylates, bioplastic, and bio-fertilizer production, ii) recovery of unexploited organic residues via anaerobic digestion to produce biogas, iii) valorization of biogenic CO2 sources, and iv) recovery of silicon from bagasse ashes.
Increased amounts of available biomass residues from agricultural food production are present widely around the globe. These biomass residues can find essential applications as bioenergy feedstock and precursors to produce value-added materials. This study assessed the production of biogenic silica (SiO2) from different biomass residues in Africa, including cornhusk, corncob, yam peelings, cassava peelings and coconut husks. Two processes were performed to synthesize the biogenic silica. First, the biomass fuels were chemically pre-treated with 1 and 5% w/v citric acid solutions. In the second stage, combustion at 600 °C for 2 h in a muffle oven was applied. The characterization of the untreated biomasses was conducted using Inductively coupled plasma—optical emission spectrometry (ICP-OES), thermal analysis (TG-DTA) and Fourier-transform infrared spectroscopy (FTIR). The resulting ashes from the combustion step were subjected to ICP, nitrogen physisorption, Energy dispersive X-ray spectroscopy (EDX) as well as X-ray diffraction (XRD). ICP results revealed that the SiO2 content in the ashes varies between 42.2 to 81.5 wt.% db and 53.4 to 90.8 wt.% db after acidic pre-treatment with 1 and 5 w/v% acid, respectively. The relative reductions of K2O by the citric acid in yam peel was the lowest (79 wt.% db) in comparison to 92, 97, 98 and 97 wt.% db calculated for corncob, cassava peel, coconut husk and cornhusk, respectively. XRD analysis revealed dominant crystalline phases of arcanite (K2SO4), sylvite (KCl) and calcite (CaCO3) in ashes of the biomass fuels pre-treated with 1 w/v% citric acid due to potassium and calcium ions present. In comparison, the 5 w/v% citric acid pre-treatment produced amorphous, biogenic silica with specific surface areas of up to 91 m2/g and pore volumes up to 0.21 cm3/g. The examined biomass residues are common wastes from food production in Africa without competition in usage with focus application. Our studies have highlighted a significant end-value to these wastes by the extraction of high quality, amorphous silica, which can be considered in applications such as catalyst support, construction material, concrete and backing material.
Porous silica was synthesized from cornhusk using the sol–gel polymeric route and compared with ash obtained from the direct combustion process under laboratory conditions. The unmodified ash from the direct combustion process was dissolved in NaOH for 1 h to form sodium silicate, which was subsequently hydrolyzed with citric acid to yield a silica xerogel. The obtained xerogel was characterized using inductively coupled plasma–optical emission spectrometry (ICP-OES), Fourier transforms infrared (FTIR) spectroscopy, X-ray diffraction (XRD), simultaneous thermal analysis (STA), gas sorption techniques to determine their elemental constituents, functional groups, crystalline phases, thermal stability, and porosity, respectively. The results showed that the synthesized silica xerogel exhibited porous network structures with a high-specific surface area and mesopore volume of 384 m2/g and 0.35 cm3/g, respectively. The pore size distribution revealed a complete transformation of the pore network structures of the unmodified ash from a monomodal to a bimodal pore system, with micro- and mesopore peaks centered around 1.5 and 3.8 nm, respectively. The ICP-OES results showed that the silica content significantly increased from 52.93 to 91.96 wt.% db after the sol–gel treatment. XRD diffraction confirmed the amorphicity of the silica particles obtained from the sol–gel extraction method. In addition, the STA data showed that the silica xerogel has high thermal stability compared to the unmodified ash, as the latter exhibited poor thermal stability and low textural properties. The high surface area and narrow pore cavity size distribution of the porous silica xerogel make it an ideal substrate for catalysts and an excellent template for growing other nanoparticles within the pores.
The synthesis and characterization of sol-gel-derived cornhusk support for low-temperature catalytic methane combustion (LTCMC) were investigated in this study. The prepared cornhusk support was impregnated with palladium and cerium oxide (Pd/CeO2) via the classical incipient wetness method. The resulting catalyst was characterized using various techniques, including X-ray diffraction (XRD), N2 physisorption (BET), transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H2-TPR). The catalytic performance of the Pd/CeO2/CHSiO2 catalyst was evaluated for methane combustion in the temperature range of 150–600 °C using a temperature-controlled catalytic flow reactor, and its performance was compared with a commercial catalyst. The results showed that the Pd/CeO2 dispersed on SiO2 from the cornhusk ash support (Pd/CeO2/CHSiO2) catalyst exhibited excellent catalytic activity for methane combustion, with a conversion of 50% at 394 °C compared with 593 °C for the commercial silica catalyst (Pd/CeO2/commercial). Moreover, the Pd/CeO2/CHSiO2 catalyst displayed better catalytic stability after 10 h on stream, with a 7% marginal loss in catalytic activity compared with 11% recorded for the Pd/CeO2/commercial catalyst. The N2 physisorption and H2-TPR results indicated that the cornhusk SiO2 support possessed a higher surface area and strong reducibility than the synthesized commercial catalyst, contributing to the enhanced catalytic activity of the Pd/CeO2/SiO2 catalyst. Overall, the SiO2 generated from cornhusk ash exhibited promising potential as a low-cost and environmentally friendly support for LTCMC catalysts.
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