Two-stage UASB reactor converting coffee drink manufacturing wastewater to hydrogen and methane

In this study, the feasibility of a continuous two-stage up-flow anaerobic sludge blanket (UASB) reactor system, consisted of thermophilic (55 °C) dark fermentative H₂ production and mesophilic (35 °C) CH₄ production from coffee drink manufacturing wastewater (CDMW), was tested. A recently proposed operational strategy was used to overcome a major drawback of the long start-up period of the UASB reactor. Firstly, a completely stirred tank reactor (CSTR) was operated for 8 days to prepare seeding. The seed was then directly transferred to the UASB reactor. Microbial aggregation took place in the initial period, and the floc size was gradually increased over time. In UASB reactor, the maximum H₂ yield of 2.57 mol H₂/mol hexose_added and a stable H₂ production rate of 4.24 L H₂/L/h were observed at a hydraulic retention time (HRT) of 6 h and substrate concentration of 20 g Carbo. COD/L. In this novel method using CDMW, thermophilic H₂-producing granules with an average particle size of 1.3 mm was successfully developed after 100 days. The more bioenergy recovery was attempted in a post-treatment process using a mesophilic UASB reactor for CH₄ production from the H₂ fermented effluent. The maximum CH₄ yield of 325 mL of CH₄/g COD was achieved with removing 93% of the COD at an organic loading rate of 3.5 g COD/L/d. The developed two-stage UASB reactor system achieved biogas conversion by 88.2% (H₂ 15.2% and CH₄ 73%) and COD removal by 98%.     

Direct fermentation of Laminaria japonica for biohydrogen production by anaerobic mixed cultures

A few studies have been made on fermentative hydrogen production from marine algae, despite of their advantages compared with other biomass substrates. In this study, fermentative hydrogen production from Laminaria japonica (one brown algae species) was investigated under mesophilic condition (35 ± 1 °C) without any pretreatment method. A feasibility test was first conducted through a series of batch cultivations, and 0.92 mol H₂/mol hexose_added, or 71.4 ml H₂/g TS of hydrogen yield was achieved at a substrate concentration of 20 g COD/L (based on carbohydrate), initial pH of 7.5, and cultivation pH of 5.5. Continuous operation for a period of 80 days was then carried out using anaerobic sequencing batch reactor (ASBR) with a hydraulic retention time (HRT) of 6 days. After operation for approximately 30 days, a stable hydrogen yield of 0.79 ± 0.03 mol H₂/mol hexose_added was obtained. To optimize bioenergy recovery from L. japonica, an up-flow anaerobic sludge blanket reactor (UASBr) was applied to treat hydrogen fermentation effluent (HFE) for methane production. A maximum methane yield of 309 ± 12 ml CH₄/g COD was achieved during the 90 days operation period, where the organic loading rate (OLR) was 3.5 g COD/L/d.     

Inhibitory effect of chloroform on fermentative hydrogen and methane production from lipid-extracted microalgae

To improve the sustainability of microalgae as a bioenergy feedstock, lipid-extracted microalgae (LEM) are often further treated by anaerobic digestion (AD). However, the residual chloroform used for extracting lipids as a solvent could inhibit this process, an aspect that has not been studied to date. In this study, the inhibitory effect of chloroform on H₂ and CH₄ production was investigated by performing batch tests. To prepare the feedstock, Chlorella vulgaris was ultrasonicated and the supernatant was discarded after centrifugation. In case of H₂ production, it was found that the H₂ yield fell to almost half that of the control (15.6 mL H₂/g COD_added) at 100 mg CHCl₃/L. The reason for the decrease of the H₂ yield with the increase of chloroform level was due to the change of metabolites from acetate and butyrate to lactate via a non-hydrogenic reaction. In comparison with H₂ production, a much more severe inhibitory effect of chloroform on CH₄ production was observed. The inhibitor concentration (IC_{30, 60, and 90}) on H₂ production was 138, 319, and 622 mg CHCl₃/L, respectively, while concentrations of 15, 37, and 86 mg CHCl₃/L were obtained on CH₄ production. When the chloroform concentration was ≥25 mg/L on CH₄ production, more than 2 g COD/L of organic acids remained, resulting in a decrease of CH₄ yield. These findings indicate that the residual chloroform in LEM should be seriously considered to prevent possible microbial inhibition when designing a process for additional energy recovery from microalgae via AD.     

A simple method to reduce the start-up period in a H2-producing UASB reactor

Introduction of an up-flow anaerobic sludge blanket (UASB) reactor apparatus to fermentative hydrogen production (FHP) enormously improves H₂ production performance. However, the long start-up period required to form H₂-producing granules (HPG) remains as a major obstacle. In the present work, a completely-stirred tank reactor (CSTR) was operated for 7 days, and the mixed liquor in the CSTR was transferred to a UASB reactor (UASBr (I)) as a seeding source. Coffee drink manufacturing wastewater (CDMW) was used as a feedstock, constituting the first attempt to form HPG from actual industrial wastewater. The strategy employed here was found to be more effective in developing HPG than directly starting from the UASB reactor (UASBr (II)), which is attributed to substantially higher active mass transfer in the CSTR. The average size of particles in the UASBr (II) blanket zone after 50 days of operation corresponded with that in the CSTR after only 7 days of operation. The drastic decrease of extracellular polymeric substance (EPS) protein concentration in the CSTR operation also indicates efficient removal of non-active biomass, the presence of which could adversely affect HPG formation. UASBr (I) showed a stable H₂ yield and H₂ production rate of 1.78 mol H₂/mol hexose_added and 2.76 L H₂/L/h, respectively, and HPG with an average size of 1.9 mm were developed after 45 days. It appears that the abundant presence of divalent ions, especially calcium ions, contained in the CDMW facilitated HPG formation.     

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.     

Application of a simple method to reduce the start-up period in a H2-producing UASB reactor using xylose

The major objective of dark fermentative H₂ production (DFHP) is the significant enhancement of the H₂ production performance from economic and engineering perspectives. An up-flow anaerobic sludge blanket (UASB) reactor based on H₂-producing granules (HPGs) has been introduced, which results in the efficiency of the H₂ production being improved significantly. However, the long start-up period remains a substantial obstacle in the stable operation of the UASB reactor. In the present study, a newly proposed operational strategy was employed to form the HPG using xylose as the feedstock, and this resulted in a successful reduction of the start-up period of the UASB reactor. After the mixed liquor in the continuously stirred tank reactor was transferred to the UASB reactor as a seeding source, the height of the HPG in the UASB reactor was progressively increased. In the UASB reactor, a maximum H₂ yield of 2.98 mol H₂/mol xylose and a stable H₂ production rate of 9.98 L H₂/L/h were observed at a hydraulic retention time of 6 h and a substrate concentration of 30 g COD/L. In this novel method, HPGs with an average particle size of 2.32 mm (0.1–4.7 mm) were successfully developed after 120 days and this is the first report documenting the successful formation of HPGs using xylose as feedstock in a UASB reactor.     

Continuous fermentative hydrogen production from coffee drink manufacturing wastewater by applying UASB reactor

The feasibility of continuous H₂ production from coffee drink manufacturing wastewater (CDMW) was tested in two different types of reactors: a completely-stirred tank reactor (CSTR) and an up-flow anaerobic sludge blanket reactor (UASBr). While the performance in CSTR was limited, it was significantly enhanced in UASBr. The maximum H₂ yield of 1.29 mol H₂/mol hexose_added was achieved at HRT of 6 h in UASBr operation. Non-hydrogenic, lactic acid was the dominant in CSTR, while butyric and caproic acids in UASBr. As caproic acid is generated by consuming acetic and butyric acids, all of which are related to H₂ production, the presence of caproic acid in the broth also indicates H₂ production, yielding 1.33 mol H₂/glucose. It was speculated that the enhanced performance in UASBr was attributed to the high concentration of biomass over 60,000 mg VSS/L in the blanket zone, which provided insufficient substrate for indigenous lactic acid bacteria (LAB) to survive. The abundance of LAB in CDMW was confirmed by natural fermentation of CDMW. That is without the addition of external inoculum, CDMW was mainly fermented into lactic acid under mesophilic condition. For the first time ever, H₂ producing granules (HPG) with diameters of 2.1 mm were successfully formed by using actual waste as a substrate.     

The use of acidified palm oil mill effluent for thermophilic biomethane production by changing the hydraulic retention time in anaerobic sequencing batch reactor

The feasibility of thermophilic biomethane production from acidified palm oil mill effluent (POME) was assessed in a 5 L anaerobic sequencing batch reactor (ASBR). The effects of various hydraulic retention time (HRT) (10-1 d) on methane production performance and the stability of ASBR in treating acidified POME were evaluated herein. It was found that the highest methane productivity of 5.65 L CH₄/L/d could be attained at HRT of 2 d. However, the removal of chemical oxygen demand (COD) and volatile fatty acid (VFA) at this HRT is rather low (65-62%) hence making it inefficient to operate at HRT 2 d since most of the contaminants remained in the liquid streams. Thus the most recommended HRT was 3 d with maximum methane productivity of 3.96 L CH₄/L/d with corresponding methane yield of 260.3 L CH₄/kgCOD_removed. The COD removal efficiency at 3 d HRT was 71%, and the VFA consumption was more than 80%. The correlation of total VFA: total alkalinity (TVFA: TA) at HRT of 3 d was found to be 0.1. This recommended HRT of 3 is equally shorter than any previously reported application of POME as a substrate for thermophilic biomethane.     

An online-monitored thermophilic hydrogen production UASB reactor for long-term stable operation

In this study, the H₂ production and chemical oxygen demand (COD) removal performances of a thermophilic upflow anaerobic sludge blanket (UASB) reactor with online monitoring system were investigated. The online monitoring system enabled a rapid monitoring and timely control of the process. As a consequence, high operating stability was achieved despite of the varied hydraulic retention time (HRT) during 310-day operation. The COD efficiency remained at above 98%, and the hydrogen yield fluctuated slightly within the range of 2.42–3.06 mol H₂ mol⁻¹ sucrose. Thermophilic H₂-producing granules were successfully cultivated in this reactor, which showed better physical and microbial properties than floc sludge and higher H₂ production rate than mesophilic granules. An analysis of the microbial growth kinetics further demonstrated a possibly higher synthesis and metabolism activity of microbes in the thermophilic granule state.     

Enhancing the performance of dark fermentative hydrogen production using a reduced pressure fermentation strategy

The partial pressure of hydrogen is an extremely important factor for hydrogen generation. This study investigated the effect of reduced pressure (via vacuum) on hydrogen production in a CSTR reactor. The results show that the reduced pressure condition is more effective in enhancing H₂ production at lower HRT (e.g., 8–4 h) than at higher HRT (e.g., 12 h). The optimal hydrogen yield and overall hydrogen production efficiency occurred at a HRT of 6 h with a value of 4.50 mol H₂/mol sucrose and 56.2%, respectively. Meanwhile, at HRT 6 h the hydrogen production rate was 0.937 mol/L/d. In addition, the HPR could be further improved to 1.196 mol/L/d when the HRT was shortened to 4 h, obtaining a 37–271% increase in HPR when compared with that described in the relevant reports. For all experiments, butyrate and acetate were the two primary soluble metabolites, accounting for 85–99% of total soluble microbial products. Predominant production of acetate and butyrate demonstrates the efficient H₂ fermentation with reduced pressure processes.     

Thermophilic hydrogen and methane production from sugarcane stillage in two-stage anaerobic fluidized bed reactors

This study evaluated the feasibility of H₂ and CH₄ production in two-stage thermophilic (55 °C) anaerobic digestion of sugarcane stillage (5,000 to 10,000 mg COD.L⁻¹) using an acidogenic anaerobic fluidized bed reactor (AFBR-A) with a hydraulic retention time (HRT) of 4 h and a methanogenic AFBR (AFBR-S) with HRTs of 24 h–10 h. To compare two-stage digestion with single-stage digestion, a third methanogenic reactor (AFBR-M) with a HRT of 24 h was fed with increasing stillage concentrations (5,000 to 10,000 mg COD.L⁻¹). The AFBR-M produced a methane content of 68.4 ± 7.2%, a maximum yield of 0.30 ± 0.04 L CH₄.g COD⁻¹, a production rate of 3.78 ± 0.40 L CH₄.day⁻¹.L⁻¹ and a COD removal of 73.2 ± 5.0% at an organic loading rate (OLR) of 7.5 kg COD.m⁻³.day⁻¹. In contrast, the two-stage AFBR-A system produced a hydrogen content of 23.9 ± 5.6%, a production rate of 1.30 ± 0.16 L H₂.day⁻¹.L⁻¹ and a yield of 0.34 ± 0.08 mmol H₂.g CODap⁻¹. Additionally, the decrease in the HRT from 18 h to 10 h in the AFBR-S favored a higher methane production, improving the maximum methane content (74.5 ± 6.0%), production rate (5.57 ± 0.38 L CH₄.day⁻¹.L⁻¹) and yield (0.26 ± 0.06 L CH₄.g COD⁻¹) at an OLR of 21.6 kg COD.m⁻³.day⁻¹ (HRT of 10 h) with a total COD removal of 70.1 ± 7.1%. Under the applied COD of 10,000 mg L⁻¹, the two-stage system showed a 52.8% higher energy yield than the single-stage anaerobic digestion system. These results show that, relative to a single-stage system, two-stage anaerobic digestion systems produce more hydrogen and methane while achieving similar treatment efficiencies.     

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.     

Carbon dioxide reforming of methane in a SrCe0.7Zr0.2Eu0.1O3−δ proton conducting membrane reactor

Utilizing CO₂ for fuel production holds the promise for reduced carbon energy cycles. In this paper we demonstrate a membrane reactor, integrating catalytic CO₂ reforming of methane with in-situ H₂ separation, that results in increased CO₂ and CH₄ conversion and H₂ production compared to a Ni catalyst alone. The tubular proton-conducting SrCe_0.7Zr_0.2Eu_0.1O_3−δ membrane reactor demonstrates that the addition of the membrane improves CO₂ conversion, due to in-situ H₂ removal, by 10% and 30% at 900 °C for CH₄/CO₂ = 1/1 and CH₄/CO₂/H₂O = 2/1/1 feed ratios, respectively. It also improves total H₂ production at 900 °C by 15% and 18% for CH₄/CO₂ = 1/1 and CH₄/CO₂/H₂O = 2/1/1, respectively. Further, the H₂/CO in the reactor side effluent can be adjusted for subsequent desired Fischer-Tropsch products by combining CO₂ reforming and steam reforming of methane.     

Biohydrogen production from palm oil mill effluent (POME) by two stage anaerobic sequencing batch reactor (ASBR) system for better utilization of carbon sources in POME

The production of biohydrogen through dark fermentation of palm oil mill effluent (POME) was evaluated in two-stages of biohydrogen in an anaerobic sequencing batch reactor (ASBR) system using enriched mixed culture for the first time. This study attempts to examine the effect of HRT and its interaction behavior with the solid retention time (SRT), and the sugar consumption. The effluent after discharged from the thermophilic reactor contained 7.61 g/L TC and 22.87 g/L TSS was fed to the secondary mesophilic reactor system. Results indicated that the overall sugar consumption reached 88.62% at the optimum HRT of 12 h with the SRT set to 20 h. The optimum hydrogen yield and HPR in the thermophilic stage were 2.99 mol H₂/mol-sugar and 8.54 mmol H₂/L·h respectively, while for the mesophilic stage were 1.19 mol H₂/mol-sugar and 1.47 mmolH₂/L·h respectively. The overall HPR showed an improvement and increase from 8.54 mmol H₂/L·h to 10.34 mmol H₂/L.h. Microbial community analysis of mixed culture in the two-stage thermophilic (55.0 °C) and mesophilic (37.0 °C) ASBR reactor was dominated by Thermoanaerobacterium sp. based on the PCR-DGGE technique.     

Rapid formation of hydrogen-producing granules in an up-flow anaerobic sludge blanket reactor coupled with high-rate recirculation

Application of an up-flow anaerobic sludge blanket (UASB) reactor to dark fermentative H₂ production greatly improves H₂ productivity due to the maintenance of high biomass concentration. However, a long start-up HRT and start-up period are required to develop the H₂-producing granules (HPGs) and to avoid washing out the suspended sludge at the start of the process. In the present work, a novel strategy to rapidly form HPGs was developed in UASB reactor. To induce highly active mass transfer in the UASB reactor, a high recirculation rate (15 times the influent) was adopted over 10 days, then recirculation was stopped. As the operation progressed, self-flocculation took place and HPGs developed after 90 h of operation. A stable production of H₂ was observed after 20 days of operation. The thickness of the HPGs layer in the sole UASB reactor increased progressively, and consequently the average HPG diameter and concentration were 1.86 mm (0.1–3.9 mm) and 52 g/L, respectively, after 60 days of operation. These findings seem to suggest that high-rate recirculation plays a crucial role in accelerating the formation of HPGs in such UASB reactors through high up-flow velocity, providing active mass transfer.     

Sequential hydrogen and methane production using the residual biocatalyst of biodiesel synthesis as raw material

Residual Fermented Solid (RFS) is the used biocatalyst obtained after enzymatic biodiesel production carried out applying the fermented solid (FS) with lipase activity. Approximately 350 g of RFS are generated for each liter of biodiesel produced from palm residues fermented solid. In this study, this residue was used for the first time as a raw material for biological hydrogen production through dark fermentation and sequential application of the hydrogen production liquid waste (HPLW) for methane obtainment via anaerobic digestion. The RFS was composed mostly of oils and fats (60% wt.%), and carbohydrates, such as mannose, glucose, and xylose. Hydrogen yield reached 239 ± 44 mL H₂/L after 24 h of fermentation using 31 g_RFS/L at the beginning of the process. Additionally, 204 ± 13 mL CH₄/g COD were produced through the anaerobic digestion of HPLW, which represented 61% of efficiency.     

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.     

La0.6Sr0.4Co0.8Ni0.2O3−δ hollow fiber membrane reactor: Integrated oxygen separation – CO2 reforming of methane reaction for hydrogen production

An integrated reactor system which combines oxygen permeable La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ (LSCN) perovskite ceramic hollow fiber membrane with Ni based catalyst has been successfully developed to produce hydrogen through oxy-CO₂ reforming of methane (OCRM). Dense La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ hollow fiber membrane was prepared using phase inversion-sintering method. OCRM reaction was tested from 650 °C to 800 °C with a quartz reactor packed with 0.5 g Ni/Al₂O₃ catalyst around the LSCN hollow fiber membrane. CH₄ and CO₂ were used as reactants and air as the oxygen source was fed through the bore side of the hollow fiber membrane. In order to gauge the effectiveness of this membrane reactor system, air flow was closed at 800 °C and dry reforming of methane (DRM) was tested for comparison. The results show that the oxygen fluxes of LSCN membrane swept by helium are nearly 3 times less than those swept by OCRM reactants. With increasing temperature and oxygen supply, methane conversion in the OCRM reactor reaches 100%, but CO₂ conversion decreases from 87% to 72% due to the competition reaction with POM. CO selectivity is as high as nearly 100% at reaction temperatures of 700 °C–800 °C while H₂ selectivity reaches a maximum of 88% at 700 °C. At 800 °C, when air supply was closed and DRM was conducted for comparison, CO selectivity decreased to 91%, resulting in carbon deposition which was around 4 times more than those obtained under OCRM reaction and H₂/CO ratio decreased from 0.93 to 0.74, showing better carbon resistance and higher H₂ selectivity of the Ni-based catalyst over the integrated oxygen separation-OCRM reaction across the LSCN hollow fiber membrane reactor.     

Effect of Ce on 5 wt% Ni/ZSM-5 catalysts in the CO2 reforming of CH4 reaction

The aim of this study is to investigate the promotional effect of Ce on Ni/ZSM-5 catalysts in the CO₂ reforming of CH₄ reaction. The evaluation of the catalytic performances of the composite catalysts was conducted in a fixed-bed reactor at atmospheric pressure. The influencing factors, including temperature, Ni and Ce loadings, molar feed ratio of CO₂/CH₄, and time-on-stream (TOS), were investigated. The characteristics of the catalysts were checked with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The reduction and the basic properties of the composite catalysts were elucidated by temperature-programmed reduction by H₂ (H₂-TPR) and temperature-programmed desorption of CO₂ (CO₂-TPD), respectively. The reactivity of deposited carbon was studied by sequential temperature-programmed surface reaction of CH₄ (CH₄-TPSR) and temperature-programmed oxidation using CO₂ and O₂ (CO₂-TPO and O₂-TPO). Results indicate that higher CH₄ conversion, H₂ selectivity, and desired H₂/CO ratio for 5 wt% Ni & 5 wt% Ce/ZSM-5 could be achieved with CO₂/CH₄ feed ratio close to unity over the temperature range of 500–900 °C. Moreover, the addition of Ce could not only promote CH₄ decomposition for H₂ production but also the gasification of deposited carbon with CO₂. The dispersion of Ni particles could be improved with Ce presence as well. A partial reduction of CeO₂ to CeAlO₃ was observed from XPS spectra over 5 wt% Ni & 5 wt% Ce/ZSM-5 after H₂ reduction and 24 h CO₂–CH₄ reforming reaction. Benefiting from the introduction of 5 wt% Ce, the calculated apparent activation energies of CH₄ and CO₂ over the temperature range of 700–900 °C could be reduced by 30% and 40%, respectively.     

Hydrogen and methane production via a two-stage processes (H2-SBR + CH4-UASB) using tequila vinasses

The feasibility of producing hydrogen and methane via a two-stage fermentation of tequila vinasses was evaluated in sequencing batch (SBR) and up-flow anaerobic sludge blanket (UASB) reactors. Different vinasses concentrations ranging from 500 mg COD/L to 16 g COD/L were studied in SBR by using thermally pre-treated anaerobic sludge as inoculum for hydrogen production. Peak volumetric hydrogen production rate and specific hydrogen production were attained as 57.4 ± 4.0 mL H₂/L-h and 918 ± 63 mL H₂/gVSS-d, at the substrate concentration of 16 g COD/L and 6 h of hydraulic retention time (HRT). Increasing substrate concentration has no effect on the specific hydrogen production rate. The fermentation effluent was used for methane production in an UASB reactor. The higher methane composition in the biogas was achieved as 68% at an influent concentration of 1636 mg COD/L. Peak methane volumetric, specific production rates and yield were attained as 11.7 ± 0.7 mL CH₄/L-h, 7.2 ± 0.4 mL CH₄/g COD-h and 257.9 ± 13.8 mL CH₄/g COD at 24 h-HRT and a substrate concentration of 1636 mg COD/L. An overall organic matter removal (SBR + UASB) in this two-stage process of 73–75% was achieved.