Bioenergy production from cotton straws using different pretreatment methods

Cotton straws are one of the most produced agricultural wastes in Turkey and getting attention by not being consumed as animal feed or an industrial stock and having a huge potential in clean energy production. In this study, different pretreatment methods for the conversion of cotton straw to sugar then biohydrogen and biomethane production from cotton straw were examined. The energy potential of cotton straw in case of an evaluation of these biomass residues was also determined using fuel cell technology. Acid pretreatment provided the highest yield in biogas formation as well as sugar extraction from the raw sample. The highest biohydrogen and biomethane production were obtained as 33 mL H₂/g VS and 83 mL CH₄/g VS, respectively. Concomitantly, the maximum power peaks in PEM fuel cell studies were observed as 0.45 W/cm² and 0.23 W/cm² with current densities of 1.086 A/cm² and 0.522 A/cm² when the fuel cell was fed with pure H₂ and biogas, respectively. This suggested that acid pretreatment is more suitable for cotton straw management in sustainable and renewable ways and the results demonstrated that PEM fuel cell is a promising clean technology for energy generation from cotton straw.     

Enhanced biohydrogen production from date seeds by Clostridium thermocellum ATCC 27405

Biohydrogen production from waste lignocellulosic biomass serves the dual purpose of converting waste into valuable products and alleviates waste disposal issues. In this study, waste date seeds were valorized for biohydrogen production via consolidated bioprocessing by Clostridium thermocellum ATCC 27405. Effect of various surfactants (PEG1000, surfactin, Triton X-100) and sodium carbonate (buffering agent) on biohydrogen production from the acid pre-treated substrate was examined. Among the various surfactants, addition of Triton X-100 resulted in the maximum biohydrogen yield of 103.97 mmol/L at an optimal dosage of 0.75% w/v. Triton X-100 supplementation favoured the production of ethanol and acetate as co-metabolites than butyrate. Addition of Na₂CO₃ to date seed fermentation medium at a concentration of 15 mM enhanced the biohydrogen production by 33.16%. Also, Na₂CO₃ buffering supported the glycolytic pathway and subsequent ethanol production than acetate/butyrate formation. Combined effect of the optimal dosages of Triton X-100 and Na₂CO₃ resulted in high hydrogen productivity up to 72 h (0.443 mmol/g h of H₂) with a total increase in hydrogen yield of 40.6% at the end of 168 h, as compared to fermentation supplemented with Triton X-100 alone. Further analysis revealed that the combined effects of the additives resulted in better substrate degradation, favourable pH window and cell growth promotion which ensured enhanced hydrogen productivity and yield. Thus, the study highlights a novel stimulatory approach for enhanced biohydrogen production from a new substrate.     

Evaluation of the biogas potential of mucilage formed in the Marmara Sea

The mucilage, which emerged as a result of increasing global warming and the deterioration of marine ecosystem balances, has taken the Marmara Sea under its influence. Mucilage appears in some periods and there is not much information about its bioenergy production potential. In this study, the biogas and biohydrogen production potential was determined when mucilage collected from the coasts is used as a substrate. Different S/X ratios were evaluated for biogas production. The highest biogas production was observed as 682 ml/g VS at the S/X ratio of 2. Dark fermentation was carried out using mixed Clostridium sp. to produce biohydrogen. As a result of fermentation, a maximum biohydrogen yield of 117 ml H₂/g VS hydrogen was obtained. In terms of both biogas and hydrogen results, the bioenergy potentials of the mucilage sample taken from the surface were determined to be higher than the bottom sediment.     

Techno-economic assessment of a synthetic fuel production facility by hydrogenation of CO2 captured from biogas

In this study, a thermodynamic and economic analysis of a synthetic fuel production facility by utilizing the hydrogenation of CO₂ captured from biogas is carried out. It is aimed to produce methanol, a synthetic fuel by hydrogenation of carbon dioxide. A PEM electrolyzer driven by grid-tie solar PV modules is used to supply the hydrogen need of methanol. The CO₂ is captured from biogas produced in an actual wastewater treatment plant by a water washing unit which is a method of biogas purification. The required power which is generated by PV panels, in order to produce methanol, is found to be 2923 kW. Herein, the electricity consumption of 2875 kW, which is the main part of the total electricity generation, belongs to the PEM system. As a result of the study, the daily methanol production is found to be as 1674 kg. The electricity, hydrogen and methanol production costs are found to be $ 0.043 kWh^?1, $ 3.156 kg^?1, and $ 0.693 kg^?1, respectively. Solar availability, methanol yield from the reactor, and PEM overpotentials are significant factors effecting the product cost. The results of the study presents feasible methanol production costs with reasonable investment requirements. Moreover, the efficiency of the cogeneration plant could be increased via enriching the biogas while emissions are reduced.     

The importance of fuel variability on the performance of solid oxide cells operating on H2/CO2 mixtures from biohydrogen processes

Biologically produced mixtures of H₂ and CO₂ (biohydrogen) from processes such as dark fermentation or photo-fermentation are versatile feedstocks which can potentially be utilised in solid oxide cell (SOC) devices. In this work, solid oxide electrolysis of biohydrogen has been investigated for the first time and is compared directly with fuel cell mode utilisation. The performance and fuel processing of SOCs utilising biohydrogen have been characterised in greater detail than has been achieved previously through the use of experiments which combine electrochemical techniques with quadrupole mass spectrometry (QMS). The effects of fuel variability on SOC overpotentials and outputs have been established and it is shown that cell performance is not significantly affected provided the fuel composition stays within 40–60 vol% H₂. QMS measurements indicate H₂O and CO production takes place in-situ via the reverse water-gas shift (RWGS) reaction. Electrical power production in fuel cell mode is predominantly through H₂ oxidation, whilst CO is converted in the WGS reaction to regenerate CO₂ but does not contribute to electrical power production. In electrolysis mode, CO is produced simultaneously through electrochemical CO₂ reduction and the RWGS reaction; H₂O is electrochemically reduced to regenerate H₂.     

Biohydrogen production from starch wastewater and application in fuel cell

Biohydrogen was produced from starch in wastewater by anaerobic fermentation. The effects of parameters, such as pH, starch concentration were investigated and optimum operating conditions were determined. The optimal pH and starch concentration for hydrogen production at 37 °C were 6.5 and 5 g/L, respectively with a maximum hydrogen yield of 186 ml/g-starch. The produced biogas contains 99% of hydrogen after passing through KOH solution to remove CO₂. The anaerobic fermentation installation was integrated with a proton-exchange-membrane fuel cell (PEMFC) system for on-line electricity generation. This combination system of biohydrogen and fuel cell achieved a power output of 0.428 W at 0.65 V per cell.     

Biological hydrogen production via dark fermentation: A holistic approach from lab-scale to pilot-scale

Biohydrogen is considered as fuel of future owing to its distinctive attribute for clean energy generation, waste management and high energy content. Suitable feedstock play important role for achieving high rate hydrogen production via dark fermentation process. In this regard, different organic wastes such as cane molasses, distillery effluent and starchy wastewater were examined as potential substrates for biohydrogen production by Enterobacter cloacae IIT-BT 08. Groundnut deoiled cake (GDOC) was considered as additional nutritional supplement to enhance biohydrogen yields. The maximum hydrogen yield of 12.2 mol H₂ kg⁻¹ COD_removed was obtained using cane molasses and GDOC as co-substrates. To further ensure reliability of the process, bench (50 L) and pilot scale (10000 L) bioreactors were customized and operated. The pilot scale study achieved 76.2 m³ hydrogen with a COD removal and energy conversion efficiency of 18.1 kg m⁻³ and 37.9%, respectively. This study provides an extensive strategy in moving from lab to pilot scale biohydrogen production thereby, providing further opportunity for commercial exploitation.     

Sequential dark–photo fermentation and autotrophic microalgal growth for high-yield and CO2-free biohydrogen production

Dark fermentation, photo fermentation, and autotrophic microalgae cultivation were integrated to establish a high-yield and CO₂-free biohydrogen production system by using different feedstock. Among the four carbon sources examined, sucrose was the most effective for the sequential dark (with Clostridium butyricum CGS5) and photo (with Rhodopseudomonas palutris WP3-5) fermentation process. The sequential dark–photo fermentation was stably operated for nearly 80 days, giving a maximum H₂ yield of 11.61 mol H₂/mol sucrose and a H₂ production rate of 673.93 ml/h/l. The biogas produced from the sequential dark–photo fermentation (containing ca. 40.0% CO₂) was directly fed into a microalga culture (Chlorella vulgaris C–C) cultivated at 30 °C under 60 μmol/m²/s illumination. The CO₂ produced from the fermentation processes was completely consumed during the autotrophic growth of C. vulgaris C–C, resulting in a microalgal biomass concentration of 1999 mg/l composed mainly of 48.0% protein, 23.0% carbohydrate and 12.3% lipid.     

The effects of fuel variability on the electrical performance and durability of a solid oxide fuel cell operating on biohythane

Biohythane is typically composed of 60/30/10 vol% CH₄/CO₂/H₂ and can be produced via two-stage anaerobic digestion of renewable and low carbon biomass with much greater efficiency compared with CH₄/CO₂ biogas. This work investigates the effects of fuel variability on the electrical performance and fuel processing of a commercially available anode supported solid oxide fuel cell (SOFC) operating on biohythane mixtures at 750 °C. Cell electrical performance was characterised using current-voltage curves and electrochemical impedance spectroscopy. Fuel processing was characterised using quadrupole mass spectroscopy. It is shown that when H₂/CO₂ is blended with CH₄ to make biohythane, the SOFC efficiency is significantly increased, high SOFC durability is achieved, and there are considerable savings in CH₄ consumption. Enhanced electrical performance was due to the additional presence of H₂ and promotion of CH₄ dry reforming, the reverse Boudouard and reverse water-gas shift reactions. These processes alleviated carbon deposition and promoted electrochemical oxidation of H₂ as the primary power production pathway. Substituting 50 vol% CH₄ with 25/75 vol% H₂/CO₂ was shown to increase cell power output by 81.6% at 0.8 V compared with pure CH₄. This corresponded to a 3.4-fold increase in the overall energy conversion efficiency and a 72% decrease in CH₄ consumption. A 260 h durability test demonstrated very high cell durability when operating on a typical 60/30/10 vol% CH₄/CO₂/H₂ biohythane mixture under high fuel utilisation due to inhibition of carbon deposition. Overall, this work suggests that decarbonising gas grids by substituting natural gas with renewably produced H₂/CO₂ mixtures (rather than pure H₂ derived from fossil fuels), and utilising in SOFC technology, gives considerable gains in energy conversion efficiency and carbon emissions savings.     

New sustainable bioconversion concept of date by-products (Phoenix dactylifera L.) to biohydrogen,biogas and date-syrup

The dates production is usually accompanied by considerable loss of fruit byproducts. The chemical analysis showed that ‘Deglet Nour’ discarded flesh is rich in soluble sugars (79.8% ± 0.8%) and fibers (12.3% ± 0.4%). A processing approach was implemented to permit the production of biohydrogen from the flesh and biogas from the crude fiber fraction after soluble sugars extraction. This approach showed interesting results since the obtained biochemical hydrogen potential and the maximum methane yield were 292 mL H₂/gVS _initial and 235 mL CH₄/gVS _fibers respectively. Parallelly, the “hot water” soluble sugar fraction (date syrup) was of interest for agro-alimentary applications and showed a high sucrose, glucose and fructose content of 33.5%, 11.8% and 13.17% respectively. This study presents a proof of concept allowing an efficient sustainable energetic conversion of the date by-products biomass to biohydrogen via dark fermentation or to soluble sugars fraction and biogas via a biorefinery approach.     

Dark fermentative biohydrogen production using pretreated Scenedesmus obliquus biomass under an integrated paradigm of biorefinery

In recent times, biohydrogen production from microalgal feedstock has garnered considerable research interests to sustainably replace the fossil fuels. The present work adapted an integrated approach of utilizing deoiled Scenedesmus obliquus biomass as feedstock for biohydrogen production and valorization of dark fermentation (DF) effluent via biomethanation. The microalgae was cultivated under different CO₂ concentration. CO₂-air sparging of 5% v/v supported maximum microalgal growth and carbohydrate production with CO₂ fixation ability of 727.7 mg L^?1 d^?1. Thereafter, lipid present in microalgae was extracted for biodiesel production and the deoiled microalgal biomass (DMB) was subjected to different pretreatment techniques to maximize the carbohydrate recovery and biohydrogen yield. Steam heating (121 °C) in coherence with H₂SO₄ (0.5 N) documented highest carbohydrate recovery of 87.5%. DF of acid-thermal pretreated DMB resulted in maximum H₂ yield of 97.6 mL g^?1 VS which was almost 10 times higher as compared to untreated DMB (9.8 mL g^?1 VS). Subsequent utilization of DF effluent in biomethanation process resulted in cumulative methane production of 1060 mL L^?1. The total substrate energy recovered from integrated biofuel production system was 30%. The present study envisages a microalgal biorefinery to produce biohydrogen via DF coupled with concomitant CO₂ sequestration.     

Whey waste as potential feedstock for biohydrogen production

In-house isolate Clostridium sp. IODB-O3 was exploited for biohydrogen production using cheese whey waste in batch fermentation. Analysis of cheese whey shows, it is enriched with lactose, lactic acid and protein components which were observed most favourable for biohydrogen production. Biohydrogen yield by IODB-O3 was compared with the cultures naturally occurring in waste solely or in combinations, and found that Clostridium sp. IODB-O3 was the best producer. The maximum biohydrogen yield obtained was 6.35 ± 0.2 mol-H₂/mol-lactose. The cumulative H₂ production (ml/L), 3330 ± 50, H₂ production rate (ml/L/h), 139 ± 5, and specific H₂ production (ml/g/h), 694 ± 10 were obtained. Clostridium sp. IODB-O3 exhibited better H₂ yield from cheese whey than the reported values in literature. Importantly, the enhancement of biohydrogen yield was observed possibly due to absence of inhibitory compounds, presence of essential nutrients, protein and lactic acid fractions which supported better cell growth than that of the lactose and glucose media. Carbon balance was carried out for the process which provided more insights in IODB-O3 metabolic pathway for biohydrogen production. This study may help for effective utilization of whey wastes for economic large scale biohydrogen production.     

Effect of fermentation conditions on biohydrogen production from lipid-rich food material

Among the basic components of organic materials, such as carbohydrate, protein, and lipid, the hydrogen yield of carbohydrate fermentation has been reported to be significantly higher than that of lipid. This study used lard as a model organic matter for lipid and investigated its H₂ production potential in batch anaerobic fermentation experiments under various combinations of stirring and CO₂-scavenging conditions. A significant increase in the hydrogen yield was observed in both CO₂-scavenging and stirring conditions; the CO₂-scavenging condition yield was 2.9 times higher than the stirring condition (116.7 and 40.3 mL H₂/g volatile solid [VS], respectively), which was much greater than reported previously. A maximal hydrogen yield of 185.8 mL H₂/g VS was obtained in the presence of both CO₂-scavenging and stirring, and the H₂ content of the total biogas was as high as 99% (v/v). In addition, there was less H₂ and more CH₄ production in the absence of CO₂-scavenging and/or stirring, which suggests that the consumption of H₂ and CO₂ for methanogenesis was the major mechanism of the poor hydrogen yield from lipid. The volatile fatty acids in all the tests consisted primarily of valeric (47.2–54.9%) and propionic acids (26.6–30.3%), and higher concentrations of these acids remained in the fermentation liquid without CO₂ removal. These results suggest that lipid-rich food waste is a potential source for H₂ production if the fermentation process is optimized to minimize the partial pressure of CO₂ and H₂ and restrain the activities of H₂-consuming bacteria.     

Biohydrogen production from autoclaved fruit and vegetable wastes by dry fermentation under thermophilic condition

Dark fermentative hydrogen production from organic waste is an attractive technique that simultaneously treats waste along with generation of renewable fuel. In this study, a relative new technology named dark dry fermentation was tested in a 55-L reactor to treat fruit and vegetable waste (FVW) along with simultaneous generation of biohydrogen. To understand the effect of autoclaving as a pretreatment method on FVW for subsequent biohydrogen production, two independent experiments were performed; one with autoclaved waste (experiment I) and another by using non autoclaved waste (experiment II). From the analyses, it was found that maximum hydrogen % obtained for experiment I was 41% (v/v%) whereas, for experiment II was 21%. In terms of total hydrogen produced, around 30% higher production was observed with experiment I compared to experiment II. The hydrogen yields for experiment I and experiment II were respectively, 27.19 and 20.81 NmL H₂/gVS (VS = volatile solid added), and the metabolites (VFAs) preferentially produced were acetic acid and iso-butyric acid.     

Comparative study on the production of biohydrogen from rice mill wastewater

This study presents the production of biohydrogen from rice mill wastewater. The acid hydrolysis and enzymatic hydrolysis operating conditions were optimized, for better reducing sugar production. The effect of pH and fermentation time on biohydrogen production from acid and enzymatic hydrolyzed rice mill wastewater was investigated, using Enterobacter aerogenes and Citrobacter ferundii. The enzymatic hydrolysis produced the maximum reducing sugar (15.8 g/L) compared to acid hydrolysis (14.2 g/L). The growth data obtained for E. aerogenes and C. ferundii, fitted well with the Logistic equation. The hydrogen yields of 1.74 mol H₂/mol reducing sugar, and 1.40 mol H₂/mol reducing sugar, were obtained from the hydrolyzate obtained from enzymatic and acid hydrolysis, respectively. The maximum hydrogen yield was obtained from E. aerogenes compared to C. ferundii, and the optimum pH for better hydrogen production was found to be in the range from 6.5 to 7.0. The chemical oxygen demand (COD) reduction obtained was around 71.8% after 60 h of fermentation.     

UASFF start-up for biohydrogen and biomethane production from treatment of Palm Oil Mill Effluent

A start-up study was conducted to produce biohydrogen and biomethane from Palm Oil Mill Effluent (POME) using a two-stage up-flow anaerobic sludge fixed-film (UASFF) bioreactor. 100% molasses was used to start the system, and POME was added at 10% increments until it reached 100% after 59 days. During this period of continuous operation, the HRT and temperature were adjusted in order to optimize the condition for biogas production. Hydrogen and methane gas production fluctuated between 53–70% and 90–95%, respectively, in the last four days of operation (days 56–59), with POME percentage being increased from 70% to 100% (30%–0% molasses). Using 100% raw POME led to a total COD removal of 83.70%, average gas production rates of 5.29 L H₂ d⁻¹ (57.11% H₂) and 9.60 L CH₄ d⁻¹ (94.08% CH₄), in their respective units. This output is comparable to, if not better than using 100% molasses as substrate. This work concludes that based on the relative consistency of biogas production on days 56–59, the two-stage UASFF bioreactor operating at a final HRT of 4 h and temperature of 43 °C has taken a period of two months for start-up.     

Biohydrogen purification using a commercial polyimide membrane module: Studying the effects of some process variables

In this work the purification of biohydrogen was attempted in mixed gas measurements using a commercial polyimide membrane module. The impact of several process variables (gas composition, temperature, ratio of retentate and feed flows) on the real separation efficiency was statistically studied applying a 3-level full-factorial experimental design. The results showed that all the factors examined could significantly affect the achievable selectivity and it was observed that the theoretical and real separation factors were remarkably different. It was also found that – in comparison with other commercially available membranes – the module reflected potential for hydrogen enrichment. Considering the design boundaries, the highest H₂/CO₂ gas selectivity (1.62) could be achieved at feed pressure, separation temperature and recovery value of ∼2.2 bar, 55 °C and 0.6, respectively, using a 65 vol% hydrogen/35 vol% carbon-dioxide binary mixture.     

Optimization of conditions for hydrogen production from complex dairy wastewater by anaerobic sludge using desirability function approach

Present study deals with the multiple-response optimization for biohydrogen production using anaerobic sludge and outstanding approach to overcome the drawbacks of conventional response surface methodology (RSM). Dairy wastewater was used as source in batch fermentation was followed for this study. Response surface methodology (RSM), based on a three level, four variable Box–Behnken design, was employed to obtain the best possible combination of substrate concentration, pH, COD/N ratio and COD/P ratio for maximum H₂ yield (HY) and specific hydrogen production rate (SHPR). Experimental data were evaluated by applying RSM integrating a desirability function approach. The optimum H₂ yield and SHPR conditions were: substrate concentration 15.3 g COD/L, pH 5.5, COD/N ratio 100.5 and COD/P ratio 120 with maximum overall desirability D of 0.94. The confirmation experiment under these optimal condition showed a HY and SHPR of 13.54 mmol H₂/g COD and 29.91 mmol H₂/g-VSS.d, respectively. This was only 0.22% and 0.20%, respectively, different from the predicted values, suggesting that the desirability function approach with RSM was a useful technique to get the maximum H₂ yield and SHPR simultaneously.     

Study on selective hydrogen sulfide removal over carbon dioxide by catalytic oxidative absorption method with chelated iron as the catalyst

H₂S is a detrimental impurity that must be removed for upgrading biogas to biomethane. H₂S removal selectivity over CO₂ employing catalytic oxidative absorption method and its influence factors were studied in this work. The desulfurization experiments were performed in a laboratory apparatus using EDTA-Fe as the catalyst and metered mixture of 60% (v/v) CH₄, 33% (v/v) CO₂ and 2000–3000 ppmv H₂S balanced by N₂ as the simulated biogas. It was found that for a given catalytic oxidative desulfurization system, it exists a critical pH, at which desulfurization selectivity achieves the highest. It was also observed that desulfurization selectivity increased along with the increase of chelated iron concentration, gas flow rate, and ratio of gas flow rate to liquid flow rate (G/L). This demonstrated that high selectivity and high efficiency for biogas desulfurization could both be achieved through optimizing these parameters. Specific to the desulfurization system of this work, when the gas flow rate was set as 1.1 L/min, after optimizing the above mentioned parameters, i.e. EDTA-Fe concentration of 0.084 mol/L, absorption solution pH of 7.8, and G/L of 55, the desulfurization selectivity factor reached 142.1 with H₂S removal efficiency attained 96.7%.     

A review on process modeling and design of biohydrogen

The current energy supply depends on fossil fuels which have increased carbon dioxide emissions leading to global warming and depleted non-renewable fossil fuels resources. Hydrogen (H₂) fuel could be an eco-friendly alternative since H₂ consumption only produces water. However, the overall impacts of the H₂ economy depend on feedstock types, production technologies, and process routes. The existing process technologies for H₂ production used fossil fuels encounter the escalation of fossil fuel prices and long-term sustainability challenges. Therefore, biohydrogen production from renewable resources like biomass wastes and wastewaters has become the focal development of a sustainable global energy supply. Different from other biohydrogen production studies, this paper emphasizes biohydrogen fermentation processes using different renewable sources and microorganisms. Moreover, it gives an overview of the latest advancing research in different biohydrogen process designs, modeling, and optimization. It also presents the biohydrogen production routes and kinetic modeling for biohydrogenation.