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.     

Hydrogen production from alcohol distillery wastewater containing high potassium and sulfate using an anaerobic sequencing batch reactor

In this study, the feasibility of hydrogen production from alcohol distillery wastewater containing high potassium and sulfate was investigated using an anaerobic sequencing batch reactor (ASBR). The seed sludge taken from an anaerobic tank treating the distillery wastewater was boiled for 15 min before being fed to the ASBR. The ASBR system was operated under different feed chemical oxygen demand (COD) values and different COD loading rates at a mesophilic temperature of 37 °C, a controlled pH at 5.5, and a cycle time of 6 cycles per day. When the studied ASBR was operated under the best conditions (providing a maximum hydrogen production efficiency) of a feed COD of 40,000 mg/l, a COD loading rate of 60 kg/m³ d, and a hydraulic retention time of 16 h, the produced gas was found to contain 34.7% H₂ and 65.3% CO_2, without any methane being detected. Under these best conditions, the specific hydrogen production rate (SHPR) of 270 ml H₂/g MLVSS d (or 3310 ml H₂/l d), and hydrogen yield of 172 ml H₂/g COD removed, were obtained. When the feed COD exceeded 40,000 mg/l, the process performance in terms of hydrogen production decreased because of the potassium and sulfate toxicity.     

Hydrogen production from cassava wastewater using an anaerobic sequencing batch reactor: Effects of operational parameters,COD:N ratio,and organic acid composition

In this work, hydrogen production from cassava wastewater using anaerobic sequencing batch reactors (ASBR) was investigated to determine the optimum number of cycles per day, chemical oxygen demand (COD) loading rate, and COD:N ratio. The system operated at a COD loading rate of 30 kg/m³d and 6 cycles per day provided maximum hydrogen production performance in terms of specific hydrogen production rate (SHPR) (388 ml H₂/g VSS d or 3800 ml H₂/l d) and hydrogen yield (186 ml H₂/g COD removed). The effect of nitrogen supplementation was also studied by adding NH₄HCO₃ into the system at the COD:N ratios of 100:2.2, 100:3.3, and 100:4.4 under the COD loading rate of 30 kg/m³d and 6 cycles per day. The maximum SHPR and hydrogen yield of 524 ml H₂/g VSS d (5680 ml H₂/l d) and 438 ml H₂/g COD removed, respectively, were obtained at the stoichiometric COD:N ratio of 100:2.2. An excess nitrogen was found to promote the productions of higher organic acids and ethanol, resulting in lowering hydrogen production efficiency.     

Biological hydrogen production in an anaerobic sequencing batch reactor: pH and cyclic duration effects

An anaerobic sequencing batch reactor (ASBR) was used to evaluate biological hydrogen production from carbohydrate-rich organic wastes. The goal of the proposed project was to investigate the effects of pH (4.9, 5.5, 6.1, and 6.7), and cyclic duration (4, 6, and 8 h) on hydrogen production. With the ASBR operated at 16-h HRT, 25 g COD/L, and 4-h cyclic duration, the results showed that the maximum hydrogen yield of 2.53 mol H₂/mol sucrose_consumed appeared at pH 4.9. The carbohydrate removal efficiency declined to 56% at pH 4.9, which indirectly resulted in the reduction of total volatile fatty acid production. Acetate fermentation was the dominant metabolic pathway at pH 4.9. The concentration of mixed liquor volatile suspended solid (MLVSS) also showed a decrease from nearly 15,000 mg/L between pHs 6.1 and 6.7 to 6000 mg/L at pH 4.9. Investigation of the effect of cyclic duration found that hydrogen yield reached the maximum of 1.86 mol H₂/mol sucrose_consumed at 4-h cyclic duration while ASBR was operating at 16-h HRT, 15 g COD/L, and pH 4.9. The experimental results showed that MLVSS concentration increased from 6200 mg/L at 4-h cyclic duration to 8500 mg/L at 8-h cyclic duration. However, there was no significant change in effluent volatile suspended solid concentration. The results of butyrate to acetate ratio showed that using this ratio to correlate the performance of hydrogen production is not appropriate due to the growth of homoacetogens. In ASBR, the operation is subject to four different phases of each cycle, and only the complete mix condition can be achieved at react phase. The pH and cyclic duration under the unique operations profoundly impact fermentative hydrogen production.     

Evolution of methane and hydrogen from ethanol wastewater with maximization of energy yield by three-stage anaerobic sequencing batch reactor system

A new anaerobic sequencing batch reactor (ASBR) unit with three stage concept was proposed and tested for spontaneous generation of hydrogen (H₂) and methane (CH₄) from ethanol wastewater with maximum energy yield. The system was controlled at 37 °C, a fixed pH of 5.5 in the first bioreactor and a recycle ratio of unity from the third bioreactor to the first bioreactor to lower the amount of sodium hydroxide for pH regulation in the first bioreactor and to increase total alkalinity and process stability. Under the optimum organic loading rate of 15 kg COD/m³d (based on the total liquid holding volume), it exhibited the highest yields and specific generation rates of both gases, resulting in the uppermost overall energy yield which was much higher than those of all other anaerobic systems. The lactic acid was found to be about 4–8 times more toxic than acetic acid to methanogens. The higher the solution pH in any anaerobic system, the greater the reduction of micronutrients.     

Biological hydrogen production from sweet sorghum syrup by mixed cultures using an anaerobic sequencing batch reactor (ASBR)

Continuous biological hydrogen production from sweet sorghum syrup by mixed cultures was investigated by using anaerobic sequencing batch reactor (ASBR). The ASBR was conducted based on the optimum condition obtained from batch experiment i.e. 25 g/L of total sugar concentration, 1.45 g/L of FeSO₄ and pH of 5.0. Feasibility of continuous hydrogen fermentation in ASBR operation at room temperature (30 ± 3 °C) with different hydraulic retention time (HRT) of 96, 48, 24 and 12 hr and cycle periods consisting of filling (20 min), settling (20 min), and decanting (20 min) phases was analyzed. Results showed that hydrogen content decreased with a reduction in HRT i.e. from 42.93% (96 hr HRT) to 21.06% (12 hr HRT). Decrease in HRT resulted in a decrease of solvents produced which was from 10.77 to 2.67 mg/L for acetone and 78.25 mg/L to zero for butanol at HRT of 96 hr-12 hr, respectively. HRT of 24 hr was the optimum condition for ASBR operation indicated by the maximum hydrogen yield of 0.68 mol H₂/mol hexose. The microbial determination in DGGE analysis indicated that the well-known hydrogen producers Clostridia species were dominant in the reacting step. The presence of Sporolactobacillus sp. which could excrete the bacteriocins causing the adverse effect on hydrogen-producing bacteria might responsible for the low hydrogen content obtained.     

Effect of hydraulic retention time on biohydrogen production from palm oil mill effluent in anaerobic sequencing batch reactor

The feasibility of hydrogen generation from palm oil mill effluent (POME), a high strength wastewater with high solid content, was evaluated in an anaerobic sequencing batch reactor (ASBR) using enriched mixed microflora, under mesophilic digestion process at 37 °C. Four different hydraulic retention times (HRT), ranging from 96 h to 36 h at constant cycle length of 24 h and various organic loading rate (OLR) concentrations were tested to evaluate hydrogen productivity and operational stability of ASBR. The results showed higher system efficiency was achieved at HRT of 72 h with maximum hydrogen production rate of 6.7 LH₂/L/d and hydrogen yield of 0.34 LH₂/g COD_feeding, while in longer and shorter HRTs, hydrogen productivity decreased. Organic matter removal efficiency was affected by HRT; accordingly, total and soluble COD removal reached more than 37% and 50%, respectively. Solid retention time (SRT) of 4-19 days was achieved at these wide ranges of HRTs. Butyrate was found to be the dominant metabolite in all HRTs. Low concentration of volatile fatty acid (VFA) confirmed the state of stability and efficiency of sequential batch mode operation was achieved in ASBR. Results also suggest that ASBR has the potential to offer high digestion rate and good stability of operation for POME treatment.     

Effect of pH on continuous biohydrogen production from liquid swine manure with glucose supplement using an anaerobic sequencing batch reactor

pH is considered as one of the most important factors governing the hydrogen fermentation process. In this project, five pH levels, ranging from 4.4 to 5.6 at 0.3 increments, were tested to evaluate the pH effect on hydrogen production from swine manure supplemented with glucose in an anaerobic sequencing batch reactor system with 16 h of hydraulic retention time (HRT). The optimal hydrogen yield (1.50 mol H₂/mol glucose) was achieved at pH 5.0 when the maximum production rate of 2.25 L/d/L was obtained. Continuous hydrogen production was achieved for over 3 weeks for pH 5.0, 4.7, and 4.4, with no significant methane produced. However, as pH increased to 5.3 and 5.6, methane production was observed in the biogas with concurrent reductions in hydrogen production, indicating that methanogens could become increasingly activated for pH 5.3 or higher. Acetate, propionate, butyrate, valerate, and ethanol were the main aqueous products whose distribution was significantly affected by pH as well.     

Enhancing biohydrogen production from chemical wastewater treatment in anaerobic sequencing batch biofilm reactor (AnSBBR) by bioaugmenting with selectively enriched kanamycin resistant anaerobic mixed consortia

The basic aim of this study was to investigate the feasibility of bioaugmentation strategy in the process of enhancing biohydrogen (H₂) production from chemical wastewater treatment (organic loading rate (OLR)—6.3 kg COD/m³-day) in anaerobic sequencing batch biofilm reactor (AnSBBR) operated at room temperature (28±2$28\pm 2$ °C) under acidophilic microenvironment (pH 6) with a total cycle period of 24 h. Parent augmented inoculum (kanamycin resistant) was acquired from an operating upflow anaerobic sludge blanket (UASB) reactor treating chemical wastewater and subjected to selective enrichment by applying repetitive/cyclic pre-treatment methods [altering between heat-shock treatment (100 °C; 2 h) and acid treatment (pH 3; 24 h)] to eliminate non-spore forming bacteria and to inhibit the growth of methanogenic bacteria (MB). Experimental data revealed the positive influence of bioaugmentation strategy on the overall H₂ production. Specific H₂ production almost doubled after augmentation from 0.297 to 0.483 mol H₂/kg COD_R-day. Chemical wastewater acted as primary carbon source in the metabolic reactions involving molecular H₂ generation leading to substrate degradation. The augmented culture persisted in the system till the termination of the experiments. The survival and retention of the augmented inoculum and its positive effect on process enhancement may be attributed to the adopted reactor configuration and operating conditions. Scanning electron microscope (SEM) images documented the selective enrichment of morphologically similar group of bacteria capable of producing H₂ under acidophilic conditions in anaerobic microenvironment. This depicted work corroborated successful application of bioaugmentation strategy to improve H₂ production rate from anaerobic chemical wastewater treatment.     

Effect of hydraulic retention time on hydrogen production and chemical oxygen demand removal from tapioca wastewater using anaerobic mixed cultures in anaerobic baffled reactor (ABR)

This study evaluated hydrogen production and chemical oxygen demand removal (COD removal) from tapioca wastewater using anaerobic mixed cultures in anaerobic baffled reactor (ABR). The ABR was conducted based on the optimum condition obtained from the batch experiment, i.e. 2.25 g/L of FeSO₄ and initial pH of 9.0. The effects of the varying hydraulic retention times (HRT: 24, 18, 12, 6 and 3 h) on hydrogen production and COD removal in a continuous ABR were operated at room temperature (32.3 ± 1.5 °C). Hydrogen production rate (HPR) increased with a reduction in HRT i.e. from 164.45 ± 4.14 mL H₂/L.d (24 h HRT) to 883.19 ± 7.89 mL H₂/L.d (6 h HRT) then decreased to 748.54 ± 13.84 mL H₂/L.d (3 h HRT). COD removal increased with reduction in HRT i.e. from 14.02 ± 0.58% (24 h HRT) to 29.30 ± 0.84% (6 h HRT) then decreased to 21.97 ± 0.94% (3 h HRT). HRT of 6 h was the optimum condition for ABR operation as indicated.     

Continuous biohydrogen production from liquid swine manure supplemented with glucose using an anaerobic sequencing batch reactor

Liquid swine manure supplemented with glucose (10 g/L) was used as substrate for hydrogen production using an anaerobic sequencing batch reactor at 37 ± 1 °C and pH 5.0 under different hydraulic retention times (HRTs). Decreasing HRT from 24 to 8 h caused an increasing hydrogen production rate from 0.05 to 0.15 L/h/L. Production rates of both total biogas and hydrogen were linearly correlated to HRT with R² being 0.993 and 0.997, respectively. The hydrogen yield ranged between 1.18 and 1.63 mol-H₂/mol glucose and the 12 h HRT was preferred for high production rate and efficient yield. For all the five HRTs examined, the glucose utilization efficiency was over 98%. The biogas mainly consisted of carbon dioxide and hydrogen (up to 43%) with no methane detected throughout the experiment. Ethanol and organic acids were the major aqueous metabolites produced during fermentation, with acetic acid accounting for 56–58%. The hydrogen yield was found to be related to the acetate/butyrate ratio.     

An anaerobic sequential batch reactor for enhanced continuous hydrogen production from fungal pretreated cornstalk hydrolysate

Anaerobic sequencing batch reactor (ASBR) process offers great potential for H₂ production from wastewaters. In this study, an ASBR was used at first time for enhanced continuous H₂ production from fungal pretreated cornstalk hydrolysate by Thermoanaerobacterium thermosaccharolyticum W16. The reactor was operated at different hydraulic retention times (HRTs) of 6, 12, 18, and 24 h by keeping the influent hydrolysate constant at 65 mmol sugars L⁻¹. Results showed that increasing the HRT from 6 to 12 h led to the H₂ production rate increased from 6.7 to the maximum of 9.6 mmol H₂ L⁻¹ h⁻¹ and the substrate conversion reached 90.3%, although the H₂ yield remained at the same level of 1.7 mol H₂ mol⁻¹ substrate. Taking into account both H₂ production and substrate utilization efficiencies, the optimum HRT for continuous H₂ production via an ASBR was determined at 12 h. Compared with other continuous H₂ production processes, ASBR yield higher H₂ production at relatively lower HRT. ASBR is shown to be another promising process for continuous fermentative H₂ production from lignocellulosic biomass.     

Optimal operational conditions for biohydrogen production from sugar refinery wastewater in an ASBR

The performance of biohydrogen production in an anaerobic sequencing batch reactor (ASBR) was evaluated with respect to variations in the key operational parameters – pH, hydraulic retention time HRT, and organic loading rate OLR using sugar refinery wastewater as substrate. Analysis of variance (ANOVA) indicated HRT had less significant influence on hydrogen content and yield in comparison to pH and OLR, whereas OLR has much impact on hydrogen production rate. Taxonomic analysis results showed that diverse bacterial species contributed to hydrogen production and the dominant species in the bioreactor were governed by all operational parameters. Even without pretreatment of the seed sludge, a high proportion of Clostridium spp. over the other bacterial species was observed at pH 5.5, and this is compatible with the high hydrogen productivity. Consequently, pH 5.5, HRT 10 h, and OLR 15 kg/m³ d were delineated as the optimal operational conditions for an ASBR fed with sugar refinery wastewater.     

Regulating biohydrogen production from wastewater by applying organic load-shock: Change in the microbial community structure and bio-electrochemical behavior over long-term operation

Detailed experiments were designed to evaluate the function of load-shock treatment strategy (50 g COD/l; 3 days) for selective enrichment of acidogenic hydrogen (H₂) producing consortia in comparison with untreated anaerobic consortia. Experiments performed in suspended-batch mode bioreactors for 520 days illustrated the relative efficiency of load-shock treated consortia in enhancing H₂ production (16.64 mol/kg COD_R) compared to untreated-parent consortia (3.31 mol/kg COD_R). On the contrary, substrate degradation was higher with control operation (ξ_COD, 62.86%; substrate degradation rate (SDR), 1.10 kg COD_R/m³-day) compared to load-shock culture (52.33%; 0.78 kg COD_R/m³-day). Fatty acid composition documented a shift in the metabolic pathway towards acetate formation after applying load-shock, which manifests higher H₂ production. Microbial profiling documented a significant alteration in species composition of microbial communities after repeated load-shock applications specific to enrichment of Firmicutes which are favourable for H₂ production. Dehydrogenase activity was stabilized with each re-treatment, signifying the adaptation inclination of the biocatalyst towards increased proton shuttling between metabolic intermediates, leading to higher H₂ production. Voltammograms of load-shock treated cultures showed a marked shift in oxidation and reduction catalytic currents towards more positive and negative values respectively with increasing scan rate evidencing simultaneous redox-conversion reactions, facilitating proton gradient in the cell towards increased H₂ production. Load-shock treatment facilitates direct cultivation of inoculums at higher substrate load without any chemical pretreatment. This study documented the feasibility of controlling microbial metabolic function by application of load-shock treatment either for preparing inoculum for startup of the reactor or to the reactor resident microflora (in situ) during operation whenever required to regain the process performance.     

Psychrophilic hydrogen production from petrochemical wastewater via anaerobic sequencing batch reactor: techno-economic assessment and kinetic modelling

Independent hydrogen production from petrochemical wastewater containing mono-ethylene glycol (MEG) via anaerobic sequencing batch reactor (ASBR) was extensively assessed under psychrophilic conditions (15–25 °C). A lab-scale ASBR was operated at pH of 5.50, and different organic loading rates (OLR) of 1.00, 1.67, 2.67, and 4.00 gCOD/L/d. The hydrogen yield (HY) progressed from 134.32 ± 10.79 to 189.09 ± 22.35 mL/gMEG_initial at increasing OLR from 1.00 to 4.00 gCOD/L/d. The maximum hydrogen content of 47.44 ± 3.60% was achieved at OLR of 4.0 gCOD/L/d, while methane content remained low (17.76 ± 1.27% at OLR of 1.0 gCOD/L/d). Kinetic studies using four different mathematical models were conducted to describe the ASBR performance. Furthermore, two batch-mode experiments were performed to optimize the nitrogen supplementation as a nutrient (C/N ratio), and assess the impact of salinity (as gNaCl/L) on hydrogen production. HY substantially dropped from 62.77 ± 4.09 to 6.02 ± 0.39 mL/gMEG_initial when C/N ratio was increased from 28.5 to 114.0. Besides, the results revealed that salinity up to 10.0 gNaCl/L has a relatively low inhibitory impact on hydrogen production. Eventually, the cost/benefit analysis showed that environmental and energy recovery revenues from ASBR were optimized at OLR of 4.0 gCOD/L/d (payback period of 7.13 yrs).     

Simultaneous biohydrogen production and starch wastewater treatment in an acidogenic expanded granular sludge bed reactor by mixed culture for long-term operation

The biofilm-based expanded granular sludge bed (EGSB) reactor was developed to treat starch-containing wastewater and simultaneously recovery hydrogen by mixed microbial culture. Granular activated carbon (GAC) was used as the support media. Operating at the temperature of 30 °C for over 400 days (data not shown), the EGSB reactor presented high efficiency in hydrogen production and COD removal ability. The maximum hydrogen production rate (HPR) was found to be 1.64 L/L.d under the organic loading rate (OLR) of 1.0 g-starch/L.d, pH of 4.42 and HRT of 4 h. The hydrogen yield (HY) peaked at 0.11 L/g-COD, under the OLR of 0.5 g-starch/L.d, pH of 3.95 and HRT of 8 h. Hydrogen volume content was estimated to be 35–65% of the total biogas. The average COD removal rate was 31.1% under the OLR of 0.125 g-starch/L.d and HRT of 24 h. The main dissolved fermentation products were ethanol, acetate and butyrate. The average attached biofilm concentration was estimated to be 8.26 g/L, which favored hydrogen production and COD removal. It is speculated that the low pH operation in the present system would contribute significantly to lower the cost of alkaline amount required for pH control in the continuous operation, especially in the scale-up biohydrogen producing system. A model, built on the back propagation neural network (BPNN) theory and linear regression techniques, was developed for the simulation of EGSB system performance in the biodegradation of starch synthesis-based wastewater and simultaneous hydrogen production. The model well fitted the laboratory data, and could well simulate the removal of COD and the production of hydrogen in the EGSB reactor.     

Hydrogen production from acid and enzymatic oat straw hydrolysates in an anaerobic sequencing batch reactor: Performance and microbial population analysis

Feasibility of hydrogen production from acid and enzymatic oat straw hydrolysates was evaluated in an anaerobic sequencing batch reactor at 35 °C and constant substrate concentration (5 g chemical oxygen demand/L). In a first experiment, hydrogen production was replaced by methane production. Selective pressures applied in a second experiment successfully prevented methane production. During this experiment, initial feeding with glucose/xylose, as model substrates, promoted biomass granulation. Also, the highest hydrogen molar yield (HMY, 2 mol H₂/mol sugar consumed) and hydrogen production rate (HPR, 278 mL H₂/L-h) were obtained with these model substrates. Gradual substitution of glucose/xylose by acid hydrolysate led to disaggregation of granules and lower HPR and HMY. When the model substrates were completely substituted by enzymatic hydrolysate, the HMY and HPR were 0.81 mol H₂/mol sugar consumed and 29.6 mL H₂/L-h, respectively. Molecular analysis revealed a low bacterial diversity in the stages with high hydrogen production and vice versa. Furthermore, Clostridium pasteurianum was identified as the most abundant species in stages with a high hydrogen production. Despite that feasibility of hydrogen production from hydrolysates was demonstrated, lower performance from hydrolysates than from model substrates was obtained.     

Hydrogen production from methane under the interaction of catalytic partial oxidation,water gas shift reaction and heat recovery

Hydrogen production from the combination of catalytic partial oxidation of methane (CPOM) and water gas shift reaction (WGSR), viz. the two-stage reaction, in a Swiss-roll reactor is investigated numerically. Particular emphasis is placed on the interaction among the reaction of CPOM, the cooling effect due to steam injection and the excess enthalpy recovery with heat recirculation. A rhodium (Rh) catalyst bed sitting at the center of the reactor is used to trigger CPOM, and two different WGSRs, with the aids of a high-temperature (Fe–Cr-based) shift catalyst and a low-temperature (Cu–Zn-based) shift catalyst, are excited. Two important parameters, including the oxygen/methane (O/C) ratio and the steam/methane (S/C) ratio, affecting the efficiencies of methane conversion and hydrogen production are taken into account. The predictions indicate that the O/C ratio of 1.2 provides the best production of H₂ from the two-stage reaction. For a fixed O/C ratio, the H₂ yield is relatively low at a lower S/C ratio, stemming from the lower performance of WGSR, even though the cooling effect of steam is lower. On the contrary, the cooling effect becomes pronounced as the S/C ratio is high to a certain extent and the lessened CPOM leads to a lower H₂ yield. As a result, with the condition of gas hourly space velocity (GHSV) of 10,000 h⁻¹, the optimal operation for hydrogen production in the Swiss-roll reactor is suggested at O/C = 1.2 and S/C = 4–6.