Currently, fossil fuels are the world’s primary form of energy. The huge consumption of fossil fuel-based energy is along with the rapid growth of the global population, which is always accompanied by growing industrialization. Excessive exploitation of fossil fuels reduces fossil fuel reserves and emits a large amount of carbon dioxide, which deepens environmental pollution and CO2-driven climate change, including global warming. Therefore, it is very necessary to develop a sustainable, economical, and eco-friendly renewable energy source as a substitute for fossil fuels to eliminate the world’s dependence on fossil fuel-based energy and alleviate the CO2-driven environmental issues.
Therefore, biohydrogen (H2) energy has attracted worldwide interest compared to other types of energy resources. It is the cleanest energy carrier, combustible with high calorific value and its combustion process produces zero carbon emissions. Therefore, producing bioH2 from a renewable resource such as agricultural waste could be a sustainable and cost-effective method for carbon neutrality. In that regard, dark fermentation (DF) has been extensively applied as a promising eco-friendly technique to produce bioH2 from lignocellulosic agricultural wastes. However, the recalcitrant and stubborn anti-degradation characteristics of the lignocellulose structure which hinder the microbial hydrolysis reactions, the proliferation of hydrogenotrophic methanogens in the formed biofilm that utilizes the generated H2 for their survival, and the accumulation of acid-rich intermediate by-products including Volatile fatty acids (VFAs) that couldn’t further be oxidized in fermentation process strictly hampered the practical application of fermentation technology for biohydrogen evolution.
To overcome the above-mentioned barriers, this study proposes a suitable pretreatment of agricultural straw waste to improve the substrate digestibility; it used thermal-pretreated activated sludge as a potential biocatalyst as a strategy to suppress methanogens and integrate microbial electrolysis cells (MEC) to dark fermentation to provide the additional energy input required for the continuous decomposition of dead-end products namely VFAs. Through bio-electrochemical processes, MEC can enhance H2 generation in the DF reactors by accelerating the decomposition of complex organic wastes including lignocellulosic agricultural wastes, and promote further utilization of the VFAs. Particularly, the applied voltage to the electrical circuit of MEC drives released electrons during the oxidation of the substrate (waste biomass) from the anode to the cathode and supports hydrogen generation at the cathode. However, to date, there is still a gap of knowledge and a lack of relevant research work exploring the feasibility of producing fermentative-bioH2 energy from real recalcitrant feedstocks without the additional use of commercial chemical catalysts. The main research results of this project are as follows:
(1) The wheat straw biomass-fed MEC performance was remarkably affected by the applied voltage. The experimental results revealed that the optimum applied voltage was 0.8V, and achieved a high H2 production which was ~28.2% and ~9.8% higher than that of 0.5V and 1V respectively. Moreover, the MEC performed under 0.8V (MEC0.8) attained a high COD removal rate of ~73.4%. Both anodic biofilm viability and microbial cell shape were less affected at low voltage but largely damaged at high voltages. The MEC (V=1.0) depicted a high charge transfer resistance of 16.06 Ω which was ~22.1% and ~73.7 % higher than that of MEC(V=0.8) and MEC(V=0.5) respectively.
(2) Using thermal-pretreated activated sludge as a potential alternative to expensive chemical catalysts and a coupled DF-MEC system significantly enhanced hydrogen production from wheat straw wastes. The overall system produced a maximum hydrogen production of 5.416 mmol H2/g straw with an energy recovery efficiency of 94.4% and a coulombic efficiency (CE) of 74%. Moreover, the DF-MEC integrated system favored the further bio-transformation of both lignocellulosic straw fibers and VFAs into biohydrogen, with 81.32% and 42.25% for COD and NH3-H removal efficiency respectively.
(3) The operating temperature of the DF-MEC integrated system significantly shaped the mixed microbial consortia structure during the conversion of lignocellulosic agricultural wheat straw biomass into biohydrogen. The results revealed that the bioreactor operating at higher temperature conspicuously promoted the thermophilic hydrogen-producing microbial growth, and the formed anodic biofilm was mainly composed of Proteobacteria (37.82%), Thermotogota (35.94%), and Coprothermobacteria (8.3%), whereas the reactors operated in the mesophilic environment was enriched more diverse microbial communities and promoted the proliferation of the methanogenic archaeal genera.
(4) Utilizing the wastewater residue from the DF-MEC process as a new potential biological fertilizer remarkably promoted plant growth. The collected bio-electrohydrogenesis left-over residues were enriched with plant growth-promoting flora including Bacillus (0.44 ± 0.11%), Azospirillum (0.11 ± 0.02%), Achromobacter (0.16 ± 0.07%), Bradyrhizobium (0.12 ± 0.02%), Allorhizobium-NeorhizobiumPararhizobium-Rhizobium (0.06 ± 0.02%), Methylobacterium-Methylorubrum (0.07 ± 0.01%), and Mesorhizobium (0.1 ± 0.03%). They also contained phosphate-solubilizing and nitrogen-fixing microorganisms as well as large amounts of nitrogen, phosphorus, potassium and other trace elements essential for plant growth. Herein, the collected DFMEC effluent was directly used to grow three plant crops including tomato, chilli and brinjal as fertilizer, and the growth and development of plants and the flowering and fruiting processes were significantly promoted. For instance, the plant heights of tomato, chilli, and brinjal species grown in the DF-MEC effluent-used protocol were ~2.03, ~1.2 and 2.7 times that of the control group, respectively.
Overall findings suggest that producing hydrogen energy using lignocellulosic straw waste as the substrate in a DF-MEC integrated system could be a promising approach to increasing the world's energy supply and reducing atmospheric greenhouse gases (GHG). Furthermore, this work provides sustainable solutions for agricultural waste management and encourages the use of the remaining generated residues as a cheap bio-fertilizer to replace the expensive commercial chemical fertilizers, thereby improving soil quality for agricultural production.