Hydrogen-methane production from pulp & paper sludge and food waste by mesophilic–thermophilic anaerobic co-digestion

The present study focused on the mesophilic anaerobic bio-hydrogen production from PPS (pulp & paper sludge) and FW (food waste), and the subsequent anaerobic digestion of the effluent for the methane production under thermophilic conditions by a two-stage process. The maximum hydrogen yield of 64.48 mL g⁻¹ VS_fed and methane yield of 432.3 mL g⁻¹ VS_fed were obtained when PPS and FW were applied with 1: 1 VS ratio as the feedstock. No VFA were cumulated in the reactor during the period of hydrogen - methane fermentation, as well as no NH₃–N and Na⁺ inhibition were found in the process. 71%–87% removal efficiencies of SCOD were attained for hydrogen and methane co-production. pH 4.8–6.4 and alkalinity 794–3316 mg CaCO₃ L⁻¹ for H₂ fermentation, as well as pH 6.5–8.8 and alkalinity 4165–4679 mg CaCO₃ L⁻¹ for CH₄ fermentation, were achieved without any adjustment. This work showed that anaerobic co-digestion of PPS and FW for hydrogen-methane co-production was a stable, reliable and effective way for energy recovery and bio-solid waste stabilization by the two-stage mesophilic–thermophilic process.     

Bioproduction of hydrogen from food waste by pilot-scale combined hydrogen/methane fermentation

A pilot-scale two-phase hydrogen/methane fermentation system generated 3.9 L biogas per unit time and reactor volume from food waste, of which the fraction of H₂ was approximately 60% at a hydraulic retention time (HRT) of 21 h. As substrate, 90% of the carbohydrates in the organic compounds were consumed, based on COD removal efficiency, and the hydrogen yield was approximately 1.82 (H₂-mol/glucose-mol). The maximum decomposition rate coefficient of hydrogen fermentation was observed at an HRT of 21 h, indicating that reducing HRTs improves hydrogen production. Over 80% of the methane was produced in the methane fermentation tank and the predominant fraction of organic acids after methane fermentation comprised acetic acid. Based on our economic evaluation, two-phase hydrogen/methane fermentation has greater potential for recovering energy than methane-only fermentation.     

Hydrogen and methane production in extreme thermophilic conditions in two-stage (upflow anaerobic sludge bed) UASB reactor system

Two-stage hydrogen and methane production in extreme thermophilic (70 °C) conditions was demonstrated for the first time in UASB-reactor system. Inoculum used in hydrogen and methane reactors was granular sludge from mesophilic internal circulation reactor and was first acclimated for extreme thermophilic conditions. In hydrogen reactor, operated with hydraulic retention time (HRT) of 5 h and organic loading rate (OLR) of 25.1 kg COD/m³/d, hydrogen yield was 0.73 mol/mol glucose_added. Methane was produced in second stage from hydrogen reactor effluent. In methane reactor operated with HRT of 13 h and OLR of 7.8 kg COD/m³/d, methane yield was 117.5 ml/g COD_added. These results prove that hydrogen and methane can be produced in extreme thermophilic temperatures, but as batch experiments confirmed, for methane production lower temperature would be more efficient.     

Production of hydrogen and methane by one and two stage fermentation of food waste

Anaerobic digestion is an attractive process for generation of hydrogen and methane, which involves complex microbial processes on decomposition of organic wastes and subsequent conversion of metabolic intermediates to hydrogen and methane. Comparative performance of a sequential hydrogen and methane fermentation in two stage process and methane fermentation in one stage process were tested in batch reactor at varying ratios of feedstock to microbial inoculum (F/M) under mesophilic incubation. F/M ratios influence biogas yield, production rate, and potential. The highest H₂ and CH₄ yields of 55 and 94 mL g⁻¹ VS were achieved at F/M of 7.5 in two stage process, while the highest CH₄ yield of 82 mL g⁻¹ VS in one stage process was observed at the same F/M. Acetic and butyric acids are the main volatile fatty acids (VFAs) produced in the hydrogen fermentation stage with the concentration range 10–25 mmol L⁻¹. Little concentrations of VFAs were accumulated in methane fermentation in both stage processes. Total energy recovery in two stage process is higher than that in one stage by 18%. This work demonstrated two stage fermentation achieved a better performance than one stage process.     

Bioconversion of de-oiled Jatropha Waste (DJW) to hydrogen and methane gas by anaerobic fermentation: Influence of substrate concentration,temperature and pH

Cellulosic materials-based de-oiled Jatropha Waste (DJW) was fermented to H₂ and CH₄ using sewage sludge inoculum. Batch assays were performed at various substrate concentrations (40–240 g/L), temperatures (25–65 °C) and pHs (5.5–7.5). The peak hydrogen production rate (HPR) and hydrogen yield (HY) of 744.0 ± 11.3 mL H₂/L-d and 10.6 ± 0.2 mL H₂/g VS obtained when the optimal substrate concentration, pH, temperature were 200 g/L, 6.5, 55 °C, respectively. The peak methane production rate (MPR) of 178.4 ± 5.6 mL CH₄/L-d obtained while DJW concentration, pH, temperature were 200 g/L, 7.0, 45 °C, however, peak methane yield (MY) of 23.3 ± 0.1 mL CH₄/g VS obtained at 40 g/L, 7.0 and 55 °C, respectively. Effect of substrate concentration on HPR and MPR was elucidated using Monod model. Butyrate and acetate were the main soluble metabolic products. Maximal carbohydrate removal and COD reduction were achieved as 51.7 ± 0.7% and 68.3 ± 1.6%, respectively.     

Biological hydrogen production by extremely thermophilic novel bacterium Thermoanaerobacter mathranii A3N isolated from oil producing well

Hydrogen producing novel bacterial strain was isolated from formation water from oil producing well. It was identified as Thermoanaerobacter mathranii A3N by 16S rRNA gene sequencing. Hydrogen production by novel strain was pH and substrate dependent and favored pH 8.0 for starch, pH 7.5 for xylose and sucrose, pH 8.0–9.0 for glucose fermentation at 70 °C. The highest H₂ yield was 2.64 ± 0.40 mol H₂ mol glucose at 10 g/L, 5.36 ± 0.41 mol H₂ mol – sucrose at 10 g/L, 17.91 ± 0.16 mmol H₂ g – starch at 5 g/L and 2.09 ± 0.21 mol H₂ mol xylose at 5 g/L. The maximum specific hydrogen production rates 6.29 (starch), 9.34 (sucrose), 5.76 (xylose) and 4.89 (glucose) mmol/g cell/h. Acetate-type fermentation pathway (approximately 97%) was found to be dominant in strain A3N, whereas butyrate formation was found in sucrose and xylose fermentation. Lactate production increased with high xylose concentrations above 10 g/L.     

A bench scale study of fermentative hydrogen and methane production from food waste in integrated two-stage process

A two-stage fermentation process combining hydrogen and methane production for the treatment of food waste was investigated in this paper. In hydrogen fermentation reactor, the indigenous mixed microbial cultures contained in food waste were used for hydrogen production. No foreign inoculum was used in the hydrogen fermentation stage, the traditional heat treatment of inoculum was not applied either in this bench scale experiment. The effects of the stepwise increased organic loading rate (OLR) and solid retention time (SRT) on integrated two-stage process were investigated. At steady state, the optimal OLR and SRT for the integrated two-stage process were found to be 22.65 kg VS/m³ d (160 h) for hydrogen fermentation reactor and 4.61 (26.67 d) for methane fermentation reactor, respectively. Under the optimum conditions, the maximum yields of hydrogen (0.065 m³ H₂/kg VS) and methane (0.546 m³ CH₄/kg VS) were achieved with the hydrogen and methane contents ranging from 29.42 to 30.86%, 64.33 to 71.48%, respectively. Biodegradability analysis showed that 5.78% of the influent COD was converted to the hydrogen in H₂-SCRD and 82.18% of the influent COD was converted to the methane in CH₄-SCSTR under the optimum conditions.     

Enhancement of hydrogen production by recycling of methanogenic effluent in two-phase fermentation of food waste

The feasibility of operational strategies was investigated for hydrogen and methane production from food waste. Food waste was heat-treated at 70 °C and fed to a two-phase anaerobic sequencing batch fermenting system. Maximum hydrogen productivity of 1.19 m³ H₂/m³ d was observed at a food waste concentration of 30 g carbohydrate/L, a hydraulic retention time of 2 d, and a solids retention time of 3.4 d. The effluent from hydrogenesis was efficiently converted to methane at an organic loading rate of up to 3.6 kg COD/m³.d. The methanogenic effluent was then recycled to the hydrogenesis reactor without any pretreatment. The recycled effluent not only successfully replaced external dilution water and decreased alkaline dosage by 75%, but also increased hydrogen production by 48%, resulting in hydrogen productivity of 1.76 m³/m³ d. The two-phase digestion with recycling would convert 91% of organic pollutants in food waste to hydrogen (8%) and methane (83%) without any external dilution water.     

Hydrogen production from alcohol wastewater by an anaerobic sequencing batch reactor under thermophilic operation: Nitrogen and phosphorous uptakes and transformation

The objective of this study was to investigate hydrogen production from alcohol wastewater using an anaerobic sequencing batch reactor (ASBR) under thermophilic operation and at a constant pH of 5.5. Under the optimum COD loading rate of 68 kg/m³d, the produced gas contained 43% H₂ without methane and the system provided a hydrogen yield and specific hydrogen production rate of 130 ml H₂/g COD removed and 2100 ml H₂/l d, respectively, which were much higher than those obtained under the mesophilic operation. Under thermophilic operation, both nitrogen and phosphate uptakes were minimal at the optimum COD loading rate for hydrogen production and most nitrogen uptake was derived from organic nitrogen. Under the thermophilic operation for hydrogen production, the nutrient requirement in terms of COD:N:P was found to be 100:6:0.5, which was much higher than that for the methenogenic step for methane production under both thermophilic and mesophilic operations and for the acidogenic step for hydrogen production under mesophilic operation.     

Lime mud from paper-making process addition to food waste synergistically enhances hydrogen fermentation performance

The effect of lime mud from paper-making process (LMP) addition on the H₂ fermentation of food waste (FW) was investigated. It was found that a slight addition of LMP (1.0–4.0 g in 200 g FW) significantly enhanced the H₂ fermentation performance, not only increasing the total amount of H₂ produced but also accelerating the whole reaction, shortening the lag period, and increasing the H₂ production rate. Fermentation stability and microbial germination were also facilitated by LMP addition. This was attributed to the existence of Ca, Fe, Mn and alkaline substances such as CaCO₃ and NaOH. The batch process treating a mixture of FW and LMP was showed that the highest hydrogen production of 137.6 mL H₂/g VS was achieved at final pH 5.0, adding 3 g LMP (in 200 g FW) to the fermentation process, which lag-phase time was about 2.5 h.     

Hydrogen production from alcohol wastewater with added fermentation residue by an anaerobic sequencing batch reactor (ASBR) under thermophilic operation

The objective of this study was to investigate the enhancement of hydrogen production from alcohol wastewater by adding fermentation residue using an anaerobic sequencing batch reactor (ASBR) under thermophillic operation (55 °C) and at a constant pH of 5.5. The digestibility of the added fermentation residue was also evaluated. For a first set of previous experiments, the ASBR system was operated to obtain an optimum COD loading rate of 50.6 kg/m³ d of alcohol wastewater without added fermentation residue and the produced gas contained 31% H₂ and 69% CO₂. In this experiment, the effect of added fermentation residue (100–1200 mg/l) on hydrogen production performance was investigated under a COD loading rate of 50.6 kg/m³ d of the alcohol wastewater. At a fermentation residue concentration of 1000 mg/l, the produced gas contained 40% H₂ and 60% CO₂ without methane and the system gave the highest hydrogen yield and specific hydrogen production rate of 128 ml/g COD removed and 2880 ml/l d, respectively. Under thermophilic operation with a high total COD loading rate (51.8 kg/m³ d) and a short HRT (21 h) at pH 5.5, the ASBR system could only break down cellulose (41.6%) and hemicellulose (21.8%), not decompose lignin.     

Effects of pretreatment methods on cassava wastewater for biohydrogen production optimization

Batch production of biohydrogen from cassava wastewater pretreated with (i) sonication, (ii) OPTIMASH BG^® (enzyme), and (iii) α-amylase (enzyme) were investigated using anaerobic seed sludge subjected to heat pretreatment at 105 °C for 90 min. Hydrogen yield at pH 7.0 for cassava wastewater pretreated with sonication for 45 min using anaerobic seed sludge was 0.913 mol H₂/g COD. Results from pretreatment with OPTIMASH BG^® at 0.20% and pH 7 showed a hydrogen yield of 4.24 mol H₂/g COD. Superior results were obtained when the wastewater was pretreated with α-amylase at 0.20% at pH 7 with a hydrogen yield of 5.02 mol H₂/g COD. In all cases, no methane production was observed when using heat-treated sludge as seed inoculum. Percentage COD removal was found to be highest (60%) using α-amylase as pretreatment followed by OPTIMASH BG^® at 54% and sonication (40% reduction rate). Results further suggested that cassava wastewater is one of the potential sources of renewable biomass to produce hydrogen.     

An integrated system for hydrogen and methane production during landfill leachate treatment

The patent-pending integrated waste-to-energy system comprises both a novel biohydrogen reactor with a gravity settler (Biohydrogenator), followed by a second stage conventional anaerobic digester for the production of methane gas. This chemical-free process has been tested with a synthetic wastewater/leachate solution, and was operated at 37 °C for 45 d. The biohydrogenator (system (A), stage 1) steadily produced hydrogen with no methane during the experimental period. The maximum hydrogen yield was 400 mL H₂/g glucose with an average of 345 mL H₂/g glucose, as compared to 141 and 118 mL H₂/g glucose for two consecutive runs done in parallel using a conventional continuously stirred tank reactor (CSTR, System (B)). Decoupling of the solids retention time (SRT) from the hydraulic retention time (HRT) using the gravity settler showed a marked improvement in performance, with the maximum and average hydrogen production rates in system (A) of 22 and 19 L H₂/d, as compared with 2–7 L H₂/d in the CSTR resulting in a maximum yield of 2.8 mol H₂/mol glucose much higher than the 1.1–1.3 mol H₂/mol glucose observed in the CSTR. Furthermore, while the CSTR collapsed in 10–15 d due to biomass washout, the biohydrogenator continued stable operation for the 45 d reported here and beyond. The methane yield for the second stage in system (A) approached a maximum value of 426 mL CH₄/gCOD removed, while an overall chemical oxygen demand (COD) removal efficiency of 94% was achieved in system (A).     

A novel method for increasing biohydrogen production from food waste using electrodialysis

The impact of continuous removal of volatile fatty acids on fermentative hydrogen production from food waste (FW) in a Continuously Stirred Tank Reactor (CSTR) was evaluated. Two experimental phases were conducted, a control phase and one in which volatile fatty acids were removed continuously from the reactor for the first time by electrodialysis (ED). Hydrogen yields were 64.7 cm³ H₂/g VS and 227.3 cm³ H₂/g VS for control phase, and ED phase respectively. Continuous removal of volatile fatty acids during fermentation not only increased H₂ yields but increased the production of volatile fatty acids (a valuable chemical feedstock) from 0.14 g/g VS to 0.34 g/g VS_.     

Effect of organic fraction of municipal solid waste addition to high rate activated sludge system for hydrogen production from carbon rich waste sludge

Municipal solid waste has been used for bio-methane production for many years. However, both methane and carbon dioxide that is produced during bio-methanization increases the greenhouse gas emissions; therefore, hydrogen production can be one of the alternatives for energy production from waste. Hydrogen production from the organic substance was studied in this study with the waste activated sludge from the municipal wastewater treatment. High rated activated sludge (HRAS) process was applied for the treatment to reduce energy consumption and enhance the organic composition of WAS. The highest COD removal (76%) occurred with the 12 g/L organic fraction of municipal solid waste (OFMSW) addition at a retention time of 120 min. The maximum hydrogen and methane yields for the WAS was 18.9 mL/g VS and 410 mL/g VS respectively. Total carbon emission per g VS of the substrate (OFMSW + waste activated sludge) was found as 0.087 mmol CO₂ and 28.16 mmol CO₂ for dark fermentation and bio-methanization respectively. These kinds of treatment technologies required for the wastewater treatment plantcompensate it some of the energy needs in a renewable source. In this way, the HRAS process decreases the energy requirement of wastewater treatment plant, and carbon-rich waste sludge enables green energy production via lower carbon emissions.     

Biohydrogen production by Thermoanaerobacterium thermosaccharolyticum TERI S7 from oil reservoir flow pipeline

Thermophilic dark fermentative hydrogen producing bacterial strain, TERI S7, isolated from an oil reservoir flow pipeline located in Mumbai, India, showed 98% identity with Thermoanaerobacterium thermosaccharolyticum by 16S rRNA gene analysis. It produced 1450–1900 ml/L hydrogen under both acidic and alkaline conditions; at a temperature range of 45–60 °C. The maximum hydrogen yield was 2.5 ± 0.2 mol H₂/mol glucose, 2.2 ± 0.2 mol H₂/mol xylose and 5.2 ± 0.2 mol H₂/mol sucrose, when the respective sugars were used as carbon source. The cumulative hydrogen production, hydrogen production rate and specific hydrogen production rate by the strain TERI S7 with sucrose as carbon source was found to be 1704 ± 105 ml/L, 71 ± 6 ml/L/h and 142 ± 13 ml/g/h respectively. Major soluble metabolites produced during fermentation were acetic acid and butyric acid. The strain TERI S7 was also observed to produce hydrogen continuously up to 48 h at pH 3.9.     

Rheological properties of hydrogen fermented food waste

Although rheological properties are essential in scaling up fermenters, there has been no report on hydrogen fermentation of organic solid wastes. In the present work, hydrogen fermentation of food waste (FW) was conducted at various substrate concentrations (10–50 g Carbo. COD/L) and operational pHs (4.5–6.5), and rheological properties were attained. High hydrogen production performance showing over 1.7 mol H₂/mol hexose_added was achieved at 10–40 g Carbo. COD/L and pH 5.5 and 6.0. The viscosity tended to increase with substrate concentration increase, and fermentation led to a significant reduction of viscosity. Before fermentation, zero viscosity and infinite viscosity of FW ranged 6.8–1274.1 mPa s and 2.2–58.1 mPa s, which were reduced to 10.4–346.2 mPa s and 1.1–5.3 mPa s after fermentation, respectively. Compared to substrate concentration, operational pH showed a less effect on rheological properties. At the similar volatile solids concentration range, hydrogen-fermented FW showed lower values of rheological properties than that of anaerobic digester sludge. Based on the agitation speed values assuring turbulent condition (complete mixing), the energy required for agitation can be reduced by 30–67% by lowering the applied agitation speed with fermentation time.     

Enhanced H2 fermentation of organic waste by CO2 sparging

This study aimed to improve the productivity of dark fermentative hydrogen production from organic waste. An anaerobic sequencing batch reactor was used for hydrogen fermentation and it was fed with food waste (VS 4.4 ± 0.2% containing 27 g carbohydrate-COD/L) at various CO₂ sparging rates (40–120 L/L/d), hydraulic retention times (HRTs; 18–42 h), and solid retention times (SRTs; 18–160 h). CO₂ sparging increased the H₂ productivity by 5–36% at all the examined conditions, confirming the benefit of the replacement of headspace gas by CO₂. The maximum H₂ production was obtained by CO₂ sparging at 80 L/L/d, resulting in the H₂ productivity of 3.18 L H₂/L/d and the H₂ yield of 97.3 mL H₂/g VS_added. Increase of n-butyrate and isopropanol yields were concurrent with the enhanced H₂ yield by CO₂ sparging. Acidogenic efficiency, the sum of H₂, organic acid, and alcohol, in the CO₂-sparged reactor ranged from 47.9 to 56.0%, which was comparable to conventional acidogenesis. Thermodynamic analysis confirmed that both CO₂ sparging and CO₂ removal were beneficial for H₂-producing reactions, but CO₂ sparing has more profound effect than CO₂ removal on inhibiting H₂-consuming reactions.     

Dark fermentation of starch factory wastewater with acid- and base-treated mixed microorganisms for biohydrogen production

Biohydrogen (Bio-H₂) can be produced from starch factory wastewater and mixed microorganisms using dark fermentation. Acidic and basic chemicals were used to treat the microorganisms to select the hydrogen (H₂)-producing culture. The experiment used a 120 mL bioreactor at 35 °C and the operation commenced with the initial pH level of wastewater in the pH range 4–7 in batch mode. The bacteria:chemical oxygen demand (COD) ratio was 0.2. The initial pH level of the wastewater in the fermentation process affected the H₂ yield and the specific hydrogen production rate (SHPR). For acid-treated bacteria, the maximum H₂ yield and SHPR were produced at an initial pH of 6.5. The maximum H₂ yield and SHPR were 138 mL/g COD degraded and 7.42 mL/g cells?h, respectively. For the base-treated bacteria, the maximum H₂ yield and SHPR were produced at initial pH of 6.5 and pH 7, respectively. The maximum H₂ yield and SHPR were 182 mL/g COD degraded and 25.60 mL/g cells?h, respectively. The COD degradation efficiency levels were 16 and 20% for acid- and base-treated bacteria, respectively. The digested wastewater remained acidic at pH 4.79–4.83. Throughout the study, no methane gas was observed in the gas mixture produced.     

Net energy gain from solid organic wastes by dark fermentation and its end products

This study evaluated the feasibility of improving net energy gain from solid organic wastes by dark fermentation (DF) and its aqueous end products. Batch experiments were conducted with dairy cattle manure as a typical solid waste blended with sucrose at different sucrose:manure ratios. This study differs from previous DF studies in two aspects; these experiments were conducted at ambient temperature without any external nutrient supplements or pH control measures while previous studies had resorted to mesophilic conditions, nutrient supplements, and external pH control; this study evaluated the feasibility of DF in terms of net energy yield rather than in terms of hydrogen yield as in previous studies. Hydrogen yields (2.9–5.3 M H₂/M sucrose) and net energy gains (2.0–3.7 kJ/g COD) demonstrated in this study are higher than in previous reports. Based on this study, sucrose:manure ratio of 4.5% is suggested as the optimal ratio.