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This study optimizes a novel surfactant-assisted green liquor dregs (GLD) pretreatment of paper mill sludge (PMS), both of which are wastes from the kraft pulping industry, using a combined Response Surface Methodology (RSM) design. Optimized conditions give a maximal reducing sugar release of 16.38 g/L. A substantial reduction in heavy metals aluminum, chromium, cobalt, arsenic, lead, and copper after pretreatment illustrates the enhancement of substrate digestibility by reducing toxic elements. Separate hydrolysis and fermentation (SHF) and simultaneous saccharification and fermentation (SSF) for hydrogen production are assessed. SSF produced a hydrogen yield of 3.72 mL/g, displaying a 36.26% increase from pretreated PMS compared to SHF. These findings provide insights into possible methods of reducing process duration, energy input, and costs incurred with waste disposal within the paper industry. Furthermore, improved hydrogen yield using an SSF process demonstrates the potential beneficiation of pulp and paper GLD and PMS wastes.

Following the example of photovoltaics, one approach to large-scale photocatalytic hydrogen production is the irradiation of a correspondingly large catalyst area. Paper production is a process in which large areas can already be produced based on the main component: cellulose. Herein, the TiO2 photocatalyst modification PC500, which also uses platinum nanoparticles as a cocatalyst, is supported in two different ways using cellulose. On the one hand, the catalyst is fixed to the surface of a commercial filter paper and, on the other hand, a photocatalytic paper is produced. For comparison, the catalyst is immobilized by means of drop coating using Nafion and measured as a suspension. The cellulose-stabilized films are active and hydrogen production is comparable with the activity obtained from the drop-coating method. The experiments show that the aggregation behavior of cellulose can be used to produce photocatalytically active films. The preparation is easy and can be applied to different kinds of (photo)catalysts. Although the films are very active, their stability during reaction due to swelling and hydrogen production must be further improved.

Biohydrogen and biomethane production via two stage sequencing system from paper mill effluent (PME) was evaluated to enhance its COD reduction. Heat-shock pretreatment of anaerobic sludge at 90 °C for 15 min was chosen to obtain a mixed microbial inoculum for dark fermentative hydrogen production. The effect of initial pH (5, 6 and 7) on the efficiency of hydrogen fermentation at different concentrations of substrate (3, 5 and 7 g-COD/L) was investigated, which the maximum hydrogen yield was obtained at initial pH 5. After that, the effects of substrate concentration (3, 5, 7, 10 and 15 g-COD/L) and fermentation temperature (37 and 55 °C) were investigated on the hydrogen production yield. The efficiency of dark hydrogen fermentation for all substrate concentrations was higher at 55 °C. The hydrogen production was enhanced as substrate concentration increased up to 5 g-COD/L, but then it was reduced, and the optimum hydrogen yield of 38.8 mL H2/g-CODinitial was obtained at substrate concentration of 5 g-COD/L at 55 °C. The highest hydrogen (35.1 mL H2/g-CODinitial) was obtained at 5 g-COD/L and 55 °C and the highest methane (553.8 mL CH4/g-CODinitial) was obtained at 3 g-COD/L and 37 °C. Maximum COD reduction of 88.1% was obtained in two-stage sequencing dark fermentation/anaerobic digestion system at 3 g-COD/L and 37 °C.

Background Up-cycling of waste papers to value-added carbon products has significant environmental and economic benefits in real life. This work aims to recycle the waste papers to construct amorphous carbon modified graphitic carbon nitride composite photocatalysts for efficient photocatalytic hydrogen generation from water under visible light. Methods Amorphous carbon (labeled as a-C) was yielded from the office waste papers by simple sulphuric-acid treatment and then combined with graphitic carbon nitride (g-CN) to form the g-CN/a-C composite photocatalysts by the thermolysis of a-C and melamine mixture. Significant Findings The addition of a-C enlarges the surface area of g-CN from 11.52 m2 g−1 of pristine g-CN to 28.12 m2 g−1 of g-CN/a-C-100. In addition, the a-C incorporation can significantly separate the electrons from the photoexcited g-CN owing to the excellent conductivity of a-C. As a result, an increased photocatalytic H2 generation was realized under visible light exposure. The g-CN/a-C-100 sample with optimized a-C contents offers the highest photocatalytic H2 generation rate of up to 17.1 μmol h−1, which is ∼12 times higher than that of pristine g-CN under the same condition. The present study manifests the great potential of the recycling of office waste papers for increased photocatalytic H2 generation.

One of the most important problems in dark fermentative hydrogen production is the need for the regulation of the ambient pH due to the formation of volatile fatty acids. For this purpose, alkaline chemicals are usually used; however, alkaline addition to the media increases salt formation, which negatively affects microbial activity. In this study, pH adjustment was performed by providing direct current as an alternative to alkali addition. Experiments were carried out batchwise and electricity was only applied to neutralize the acidic pH value. The waste paper hydrolysate was used as a substrate and the effects of applied voltage (0.25-3 V), substrate concentration (4.8-41.2 g/L at 1 V) and electrode distance (0.3-1.3 cm at 1 V) on hydrogen production performance was investigated. Voltages less than 1 V required too much time to keep the pH convenient and voltages more than 1.5 V adversely affected hydrogen production performance. Providing direct current to the fermentation media significantly reduced the adaptation phase. Conditions for optimal pH adjustment and hydrogen production were obtained at 1 V, 20 g glucose/L and 0.5 cm electrode distance. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The present work focused in assessing the hydrogen production from pretreated wastes of the paper industry (PIW) by simultaneous saccharification and fermentation (SSF) using anaerobic biofilms developed in natural fibers (ixtle) at different conditions. Anaerobic sludge from brewery wastewater treatment was used for biofilms and they were developed in plastic spheres covered with fiber cord from ixtle. The solid wastes of paper industry were previously pretreated with H2SO4 at 2.5% (v/v) at 120 °C by 30 min. The solids pretreated were hydrolyzed and fermented in batch reactors. All reactors were kept at an initial pH of 5.0 and three levels of enzyme loadings (10, 40 and 70 FPU/mL) and temperatures (35, 45, 55 °C) were assessed. The maximum hydrogen obtained (60.75 mmol/h*g volatile solids) was at 45 °C and 70 FPU/mL, moreover, no methane was detected in all cases.

Paper industries are water-intensive industries that produce large amount of wastewater containing dyes, toxicity and high nutrient content. These industries require sustainable technology for their waste disposal and MEC could be one of them. However, effective MEC operation at neutral pH and ambient temperature requires economical and efficient cathodes that are capable to treat indusial wastewater along with recovery of energy/biohydrogen. Co-deposits of Nickel, Nickel–Cobalt and Nickel–Cobalt–Phosphorous on the surface of SS and Cu base metals distinctly were used as cathodes in MEC for the concurrent treatment of real paper industry wastewater and biohydrogen production. MECs were utilized in batch mode at neutral pH, applied voltage of 0.6 V and 30 ± 2 °C temperature with paper industry wastewater and activated sludge as microbial sources. The fabricated Nickel–Cobalt–Phosphorous gives the higher hydrogen production rate of 0.16 ± 0.002 m3(H2) m−3d−1 and 0.14 ± 0.002 m3(H2) m −3d −1 respectively, with ~33–42 % treatment efficiency for a 500 ml wastewater in 7-day batch cycle in both the cases; while it is lowest in the case of the control cathodes (SS1 (0.07 ± 0.002 m3(H2) m−3d−1) & Cu1 (0.06 ± 0.004 m3(H2) m−3d−1)). It was also found that fabricated cathodes have the capability to treat industrial wastewater at ambient conditions efficiently with higher energy recovery. Prepared cathodes show enhanced hydrogen production and treatment efficiency as well as are competitive to some reported literature.

In this study, microbial electrolysis cells (MECs) are used for the treatment of actual paper and pulp industry wastewater and production of biohydrogen, for the evaluation of economical and low-cost cathodes. Nickel, nickel–cobalt and nickel–cobalt–phosphate electroplating on SS and Cu rod are explored as-fabricated cathode catalysts in MECs for the estimation of their electrocatalytic activity in terms of energy recovery and treatment efficiency using paper–pulp industry real wastewater. Developed cathodes are explore in MECs in a controlled temperature of 30 ± 2 °C, under applied voltage of 0.6 V at neutral pH with paper–pulp industry wastewater and activated sludge as inoculum. Simultaneous treatment of paper–pulp industry wastewater with hydrogen production rates (1.1–3.87 m3/m3-d) and 54–64% of initial COD removal. Obtained results suggest that fabricated cathodes have potential to become alternative to Pt. for the treatment of real industrial wastewater using MECs. It also indicates that the hydrogen production and MECs performance greatly depend on the composition of wastewater and inoculum. MECs performances were evaluated in terms of hydrogen production rate, columbic efficiencies, overall energy efficiency and volumetric current density.

Reforming of hydrocarbon which is an important hydrogen production method proceeds in two steps, i.e. steam reforming and shift reaction. Due to different thermodynamics, the two reactions are conventionally conducted at different temperatures. This study examines one step methane reforming by use of proton-conducting electrochemical cell in combination with a reforming catalyst. Promotion of the reforming reaction was intended by extracting hydrogen via electrochemical hydrogen pumping with a proton conductor cell. In order to compensate for the slow kinetics of the steam reforming, a paper catalyst loaded with Ni was placed in front of the electrochemical cell. Electrolyte support cells were used to verify this concept, and the effect of the electrochemical hydrogen pump was investigated from the composition of the outlet gas. Electrode support cells using a thin film electrolyte was used to reduce overvoltage. It is demonstrated that the steam reforming reaction and the shift reaction take place in one electrochemical cell. Effective catalyst placement and energy efficiency is discussed.

Growth properties, oxidation-reduction potential kinetics and hydrogen production of Escherichia coli BW25113 parental strain (PS) and hydrogenase (Hyd)-negative mutants were investigated after fermentative growth using office paper waste and cardboard (PW) hydrolysate (PWH). PWH was obtained by using dilute acid method in a steam sterilizer for 1 h, 121 °C. Optimal conditions for bacterial growth and H2 production were identified (PWH concentrations, pH 7.5). Recording of redox potential using a platinum electrode revealed a drop to −500 ± 10 mV, with a H2 yield of ~1.45 mmol H2 L−1 after 4 h of growth using PWH resulted in the formation of 0.20 ± 0.02 g bacterial cell dry weight L−1. Bacterial biomass formation was stimulated ~3-fold upon addition of 0.5% yeast extract, and H2 production started early - at the beginning of the exponential phase. Moreover, mutants lacking Hyd-1 and Hyd-2 significantly enhanced H2 production. The findings would be beneficial for the development of H2 production biotechnology using cheap solid waste materials.

Two temperature-phased anaerobic digestion (TPAD) systems (55 °C in the first reactor and 35 °C in the second reactor) with and without recirculation were operated in parallel for the co-digestion of food waste and paper waste. A long-term experiment was carried out for these two systems with the paper waste ratios elevated from 0 to 50%. The removal efficiencies of COD, TS, VS, carbohydrate and protein in the recirculated TPAD system were higher than those of the non-recirculated system. The successful acclimation of thermophilic cellulose-degrading bacteria in the first reactor (RT1), partly due to recirculation, ensured the effective degradation of cellulose when the paper waste ratio was higher than 40%, resulting in the production of large amounts of hydrogen in reactor RT1. In the absence of recirculation, the main substance produced in the first reactor of the non-recirculated system (T1) was lactic acid. This gradually led to over-acidification and a low degradation efficiency and no methane or hydrogen was produced in T1. Recirculation helped to establish a stable bacterial community capable of producing bio-hydrogen in reactor RT1. The relatively low pH of 5.5 in the RT1 inhibited the activity of hydrogenotrophic archaea without consuming hydrogen, facilitating high hydrogen production levels.

In this research, we carried out the process of simultaneous saccharification and fermentation (SSF) of paper industry wastes with/without chemical pretreatment, using reactors in batch with anaerobic biofilms developed in spheres covered with ixtle fiber cord. Biofilms were previously developed a UASB reactor using anaerobic sludge with acid/thermal pretreatment to remove hydrogen consuming bacteria. Subsequently, the process of saccharification and simultaneous fermentation (SSF) of paper industry waste without chemical pretreatment was evaluated using batch reactors with developed anaerobic biofilms. The key process parameters were: pH (4, 5 and 6) and enzyme loading of Celluclast enzyme (10, 40 and 70 FPU) at a temperature of 45° C The results for hydrogen production with paper industry wastes without pretreatment showed optimal working conditions to maximize hydrogen production by SSF process at: pH (5) and an enzyme load of 70 FPU, so the maximum hydrogen yield obtained was 31.188 mmol/h × gSV. The results obtained from the evaluation of the process of SSF performed with paper industry wastes subjected to chemical pretreatment with H 2 SO 4 2.5% showed the optimum working conditions to maximize hydrogen production: pH (4), an enzyme load of 70 FPU, the maximum value of hydrogen yield obtained was 55 844 mmol/h *gSV. The key process parameters were optimized by the response surface methodology (RSM) based on a two factor-three level central composite design (CCD), using as variables: pH (4.5 and 6), enzyme loading of Celluclast ® (10, 40 and 70 UPF) and temperature (45 °C), for paper industry wastes with/without acid pretreatment. The results showed the analysis of variance was performed to test the importance of the polynomial equation of second order, so equations obtained for both residues (with/without pretreatment) describe the hydrogen yield in this study.

In this work, a paper-based hydrogen fuel cell is developed without the need for hydrogen storage. Instead, an embedded aluminum foil inside the paper is utilized for in-situ hydrogen generation. The electrodes and current collectors are also deposited on the paper, leading to a lightweight, compact and flexible hydrogen fuel cell with an OCV reaching 0.93 V and a peak power density of 4 mW cm−2. Benefited from the impeded hydroxyl ion diffusion, the hydrogen generation rate is well controlled, leading to a high faradaic efficiency of 72%. In addition, the cell can be operated under different bending angles with negligible power loss. Furthermore, it can be conveniently stacked in the same piece of paper for higher voltage and power outputs. Such a novel fuel cell design is especially suitable for powering various flexible devices with small rated power.

The effects of N/C, P/C and Fe/C ratios on dark fermentative hydrogen gas production from activated carbon treated WPT hydrolysate were investigated using Box-Behnken statistical experiment design. N/C, P/C and Fe/C ratios were chosen as independent variables while the H-2 yield and SHPR were set as the objective functions. H-2 yield and SHPR functions were described by two quadratic model functions. The addition of a proper amount of N, P and Fe to the fermentation media was found to be essential to enhance the H-2 production performance. Linear and interaction terms of N/C and Fe/C did have a significant effect on the H-2 yield in the model function. However, the SHPR was significantly affected by the linear and interaction terms of N/C and P/C. The most convenient N/C, P/C and Fe/C ratios resulting maximum H-2 yield (0.656 mol H-2/mol glucose) and SHPR (241.64 mL H-2/g biomass.h) were determined as 0.05, 0.09 and 0.003 (w/w), respectively. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm−2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec−1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.

Photocatalytic hydrogen evolution from water splitting, using paper as an electron donor, was achieved upon the use of a hybrid photocatalyst of mesoporous TiO2 decorated with Ni nanoparticles. Through the involvement of a Ni cocatalyst, the separation and migration of photo-generated electrons in TiO2–Ni hybrids were significantly enhanced. The soluble paper in alkaline solution played the role of a sacrificial electron donor by reacting with hydroxyl radicals generated from hole oxidation with OH−. These findings provide an inexpensive route to drive aqueous proton reduction to hydrogen through waste biomass oxidation.

This study presents dark fermentative hydrogen gas production from acid hydrolysed waste paper towel hydrolysate. Firstly, Box-Behnken statistical experiment design was used to investigate glucose production from waste paper towel by acid hydrolysis. S/L ratio, hydrolysis time and pH were chosen as independent variables while glucose concentration in the hydrolysate was the objective function. Highest glucose concentration of 32.17 g/L was obtained at S/L ratio of 100 g/L, pH 0 (gauge pH) and 180 min hydrolysis time. All variables were found to have significant effect on glucose formation. Glucose concentration increased by increasing the S/L ratio and hydrolysis time, but decreased by increasing the pH. Secondly, the hydrolysate obtained at most convenient hydrolysis conditions was subjected to lime putty treatment for the removal of 5-HMF and SO4 2-. Thirdly, H2 gas was produced from the detoxified hydrolysate by dark fermentation. Maximum H2 formation yield, rate and H2 percentage in the gas phase were 1.02 mol H2/mol glucoseconsumed, 130.22 mL H2/g biomass.h and 43%, respectively. The remaining 5-HMF after lime treatment was effectively removed in dark fermentation. © 2017, Springer Science+Business Media Dordrecht.

Energy-saving electrolytic hydrogen production is the precondition for implementing large-scale hydrogen energy exploitation. Replacing the sluggish water oxidation reaction with thermodynamically more favorable pollutant electro-oxidation (degradation) is a very promising approach to combine energy-efficient hydrogen production and sewage treatment. Herein, a homologous asymmetrical two-electrode configuration, made up of self-assembly induced mosslike Fe2O3 and FeP on electro-oxidized carbon paper (ECP), was used to electrolyze the integrated hydrazine oxidation–hydrogen evolution system. The free-standing Fe2O3/ECP electrode was fabricated by pyrolyzing iron phthalocyanine/ECP self-assembly in air and serves as an anodic reaction catalyst. Subsequent phosphidation of the Fe2O3/ECP leads to the formation of the FeP/ECP catalyst for hydrogen evolution reaction. The cross-linked mosslike Fe2O3 and FeP nanoparticles densely covered on the surface of ECP provide richly exposed catalytic sites and the well-d...

The feasibility and performance of hydrogen production from paper sludge without inoculation was investigated under thermophilic conditions. The maximum hydrogen production reached 64.32 mM with 7.4% PS. The dynamic changes in bacterial community structures during hydrogen production were investigated by analyzing 16S rDNA gene sequences using high throughput sequencing technology. The results showed that microbial community was dominated by order Clostridiales and Thermoanaerobacterales. Genus Thermoanaerobacterium and Ruminiclostridium played a leading role in the fermentation process, which was responsible for the hydrolysis of PS and hydrogen production. Effect of inoculation with Clostridium thermocellum on hydrogen production from PS was also studied. The results showed that C. thermocellum supplement significantly increased hydrogen yield and holocellulose degradation rate by 96.80% and 32.95%, respectively. In addition, inoculation of C. thermocellum enhanced VFA generation and shortened the lag phase of hydrogen production. The present study lays the foundation on the valorization of waste lignocellulose.

Urgent need for waste disposal and renewable energy have opened up promising pathways for renewable and sustainable fuel production to substitute traditional fossil fuels. In this study, catalytic co-pyrolysis of waste paper (WP) and polyvinyl chloride (PVC) as typical municipal solid wastes was experimentally investigated towards hydrogen-rich syngas production. Results indicated the maximum H2 yield (429 μmol·gcat−1·min−1) was obtained with 60% PVC weight ratio under 900 °C which was higher than single component pyrolysis. Higher hydrogen yield (681.76 μmol·gcat−1·min−1) appeared over Fe/CeO2–CaO under the optimal conditions compared to that of Ru/ZSM-5-CaO (445.54 μmol·gcat−1·min−1). From the calculated non-isothermal kinetic parameters, both catalysts could reduce activation energies. Proper porous structure and CaO content in the catalyst could enhance hydrogen production via carbon species fixation.

Gassing problems and premature insulation failures in wind turbine transformers indicate reliability concerns about the insulation of such components. This fact necessitates investigating degradation of transformer insulation systems under high-dV/dt pulse voltages that exist in today's wind energy plants. For this purpose, PD activity, generally assumed to be the main long-term cause of insulation deterioration, needs to be analyzed. This work evaluates the effects of impulse voltage parameters such as rate of rise and repetition frequency on inception voltage and intensity of PD activities. PD parameter measurement under high-dV/dt voltages is challenging due to interferences from fast oscillations, and difficulties of PD energy measurements. To avoid such issues, which are related to electromagnetic detection methods under pulse energization, this work uses a chemical approach to compare PD activities, based on the rate of hydrogen generation in a controlled test chamber with oil/paper samples. Gas monitoring of the oil containing impregnated paper samples reveals that a faster rate of rise increases PD energy as well as inception voltage. Results based on experiments conducted in small oil chambers show good correlation between the amount of hydrogen detected and PD energy level; hence it can be used as a benchmark for comparing PD energy levels under various impulse waveforms.

Creating efficient hydrogen production properties from the macroscopic assembly of two-dimensional materials is still an unaccomplished goal. Here we report a facile route to fabricate a flexible MoS2/PtNPs/SWCNT paper with an ultralow onset potential of -35 mV, a Tafel slope of 39.6 mV per decade and over 60 h of electrochemical durability.

This work demonstrates a stand-alone power source that integrates a paper-based hydrogen fuel cell with a customized chemical heater that produces hydrogen in-situ upon the addition of a liquid. The presented approach operates by capillary action and takes advantage of the hydrogen released as a by-product of an exothermic reaction used in point-of-care diagnostics. The paper-based fuel cell produces a maximum power of 25.8 mW (103.2 mW cm−2), which is suitable for powering a diversity of electrical devices such as commercially available digital pregnancy tests and glucometers. While device shape and dimensions can be customized, here it is shown that the fuel cell can be designed in a compact form factor and footprint comparable to a lateral flow test while providing a remarkable power output. This approach holds great promise for powering portable diagnostics, as the generated electric power could enable device functionalities required for advanced assays, such as device timing, actuation, and signal quantification. Part of the same liquid sample that is to be analyzed (urine, saliva, water, etc) could be used to trigger the hydrogen generation and start the fuel cell operation., J.P. Esquivel acknowledges support from Marie Curie International Outgoing Fellowship (APPOCS - GA.328144) within the 7th European Community Framework Programme. J. Buser and P. Yager were supported by a grant from DARPA DSO/BTO--HR0011-11-2-0007, awarded to Yager at the University of Washington. P. Yager was supported in part by funds from the Department of Bioengineering at the University of Washington. S. Rojas acknowledges financial support from project ENE2013-42322R. N. Sabaté would like to thank financial support received from ERC Consolidator Grant (SUPERCELL - GA.648518).

Biogas-powered fuel cells that use low-quality biogas produced from organic waste hold a great promise for providing ultra-clean electric energy with on-site power generators. However, natural biogas contains a small amount of H2S, which causes a rapid deactivation of steam-reforming metal catalysts, such as Ni. In this work, we successfully prepared two types of paper-structured catalyst, separately containing manganese oxides (MnO x ) and nickel/magnesium oxides (Ni/MgO), for desulfurization and methane-steam reforming, respectively. In the sequential desulfurization and methane-steam reforming, paper catalyst assembly, designed by stacking MnO x papers upstream and Ni/MgO papers downstream in a dual-layered form, enabled continuous hydrogen production from simulated biogas containing ca. 2000 ppm H2S impurities, whereas single-layered Ni/MgO papers immediately lost their catalytic activity due to the H2S poisoning. This combination of flexible, stackable, and easy-to-handle paper-structured catalysts has the potential to improve the energy efficiency and to process economics of providing hydrogen to biogas-powered fuel-cell systems.

The population explosion and exponential increase in energy demand of the world have created enormous stress on finite fossil fuels and posed a threat to the environment. The sustainable Bio-Electrochemical Systems which include Microbial Fuel Cells (MFC), Microbial Electrolysis Cells (MEC) etc. can generate energy from waste. The present study has intended to utilize Sewage sludge (SS), Compost leachate (CL), and Mess Food waste (FW) as an organic substrate in an Integrated Bio-Electrochemical system to evaluate the bioelectricity generation potential in dual-chambered H type MFCs, then utilization of digestate from MFCs for Bio-hydrogen production in MECs. The maximum open-circuit voltages of 595 mV, 505 mV, and 690 mV were recorded in SS, CL, and FW fed MFC respectively, and their corresponding peak power densities of 1.8 ± 0.1 W/m2, 1.3 ± 0.1 W/m2 and 2.4 ± 0.1 W/m2 respectively were generated. The COD removal of 62.37%, 66.8%, and 50.19% were achieved for MFC fed with SS, CL, and FW respectively. The digestate fed MECs had further shown COD removal of 55.26%, 64.40% and 46.61% of the digestate in the "MFC turned MEC" system. The corresponding volumes of gas produced per gram of COD removal were reported as 23.8, 18.1 and 55.1 for SS, CL and FW respectively. The overall COD removal by bio-electrochemical system (BES) of 83.25%, 88.23 % and 73.41% for SS, CL and FW were achieved. The higher OCV of 690 mV and 55.1 mL of bio-hydrogen per gram of the COD removed has suggested the suitability of the FW for Integrated Biochemical system. . The comparative higher performance of FW as feeds has established itself as a potent choice for bio-electricity and bio-hydrogen production.

Waste paper was evaluated for hydrogen gas production by sequential dark fermentation and electrohydrolysis. Acid hydrolysed waste paper towel hydrolysate was first subjected to dark fermentation to determine the most suitable initial biomass concentration. The effects of initial biomass concentration was investigated at constant substrate concentration by varying the biomass concentration between 0 and 6 g/L and the most suitable hydrogen production was obtained at 0.10 g/L. Then effects of initial substrate concentration was investigated at 0.10 g/L initial biomass concentration by varying the glucose concentration between 5 and 40 g/L. 21.33 g glucose/L resulted in the highest hydrogen formation yield and rate in the second set of experiments. When the effluent of dark fermentation operated at optimum initial biomass and substrate concentration was subjected to electrohydrolysis the overall hydrogen production of the sequential process was 30.12 mL H2/mL. © 2015 Hydrogen Energy Publications LLC.

Torrefaction is a pretreatment method that converts biomass to a fuel-like substance that can replace coal for sustainable power generation. In this work, a thermodynamic-based process simulation model was developed to simulate the gasification of empty fruit bunch (EFB), with torrefaction as pretreatment, to determine the optimum conditions; equivalence ratio, reactor temperature, torrefaction medium concentration, steam-to-biomass (S/B) ratio and system configuration were studied to determine their influence on hydrogen concentration, higher heating value (HHV), syngas ratio and cold gas efficiency (CGE). The highest hydrogen yield was obtained at an S/B ratio of 1.3 at 800 °C, with a syngas ratio of 2.5 and a CGE of 84%. Concentration of torrefaction medium showed no effect on hydrogen concentration due to the simplicity of the model used, but work is in progress in this direction. Therefore, steam gasification is more suitable than air gasification in hydrogen production.

This research aims to evaluate the hydrogen production and removal ability of impurity (e.g. tar and NH3) generated from sewage and textile sludge co-gasification using lab-scale fluidized-bed gasifier with an integrated hot-gas cleaning system. The gasification temperature and equivalence ratio (ER) were controlled at 850 °C and 0.2, as well as the hot gas cleaning system operated at 250 °C with the combination of zeolite, calcined dolomite, and activated carbon. Experimental results indicated that the H2 and CO yield in co-gasification of the tested sludge ranged from 2.12 to 2.45 mol/kg and from 2.83 to 3.98 mol/kg, respectively. The overall energy content of produced gas ranged between 2.40 and 2.63 MJ/kg, and cold gas efficiency (CGE) was nearly 15%. The impurities of produced gas were effectively mitigated by the hot-gas cleaning system, which could remove approximately 90% of the heavy fraction tar, up to 77% of total tar, and about 35% of ammonia. In summary, the combination of the fluidized-bed gasifier and the hot-gas cleaning system had been well developed for purifying the syngas produced from the tested sludge, and it could be applied to other organic wastes in the future.

The development of an effective, non-precious electrocatalyst for the hydrogen evolution reaction (HER) is highly desirable for the commercial application of hydrogen as a clean and renewable energy and remains a substantial challenge. Herein, a hierarchical nanowires array (HNA) of iron phosphide (FeP) nanowires coated with iron phosphide nanorods grown on a carbon fiber paper (CFP) was constructed which exhibited remarkable catalytic activity in the HER. The overpotential required for the current density of 20 mA cm−2 is as small as 45 and 221 mV in acidic and basic solution, respectively, corresponding to Tafel slopes of 53 and 134 mV dec−1. The effective catalytic activity of the CFP–FeP HNA in the HER, together with its long-term stability and nearly 100% faradaic efficiency in water electrolysis, make the CFP–FeP HNA one of the best non-noble electrocatalysts described to date. The prominent catalytic activity of CFP–FeP HNA is correlated to the large number of active sites for the HER, and the fast electron transport from the CFP to the FeP nanorods mediated by FeP nanowires.

Dark anaerobic fermentation is an interesting alternative method for producing biohydrogen (H(2)) as a renewable fuel because of its low cost and various usable organic substrates. Pulping sludge from wastewater treatment containing plentiful cellulosic substrate could be feasibly utilized for H(2) production by dark fermentation. The objective of this study was to investigate the optimal proportion of pulping sludge to paper waste, the optimal initial pH, and the optimal ratio of carbon and nitrogen (C/N) for H(2) production by anaerobic seed sludge pretreated with heat. The pulping sludge was pretreated with NaOH solution at high temperature and further hydrolyzed with crude cellulase. Pretreatment of the pulping sludge with 3% NaOH solution under autoclave at 121 °C for 2 h, hydrolysis with 5 FPU crude cellulase at 50 °C, and pH 4.8 for 24 h provided the highest reducing sugar production yield (229.68 ± 2.09 mg/g(TVS)). An initial pH of 6 and a C/N ratio of 40 were optimal conditions for H(2) production. Moreover, the supplement of paper waste in the pulping sludge enhanced the cumulative H(2) production yield. The continuous hydrogen production was further conducted in a glass reactor with nylon pieces as supporting media and the maximum hydrogen production yield was 151.70 ml/g(TVS).

Supercritical water gasification (SCWG) is a method by which biomass can be converted into a hydrogen-rich gas product. Wet industrial waste streams, which contain both organic and inorganic material, are well suited for treatment by SCWG. In this study, the gasification of two streams of biomass resulting from the pulp and paper industry, black liquor and paper sludge, has been investigated. The purpose is to convert these to useful products, both gaseous and solids, which can be used either in the papermaking process or in external applications. Simple compounds, such as glucose, have been fully gasified in SCWG, but gasification of more complex compounds, such as biomass and waste, have not reached as high conversions. The investigated paper sludge was not easily gasified. Improving gasification results with catalysts is an option and the use of alkali salts for this purpose was studied. The relationship between alkali concentration, temperature, and gasification yields was studied with the addition of KOH, K2CO3, NaOH and black liquor to the paper sludge. Addition of black liquor to the paper sludge resulted in similarly enhancing effects as when the alkali salts were added, which made it possible to raise the dry matter content and gasification yield without expensive additives.

Hydrogen is a renewable gas, efficient to produce energy that makes it a suitable alternative and effective solution for a carbon-free environment. Unlike other fossil fuels, combustion of hydrogen does not produce toxic compounds, such as greenhouse gases, carbon monoxide, hydrocarbons, etc., resulting in less environmental pollution. Agro-industrial residues contain several lignocelluloses that favor the growth of microorganisms to produce valuable products such as hydrogen. Of the diverse techniques in hydrogen production, bioconversion proves to be an efficient method in permuting agro-industrial residues into hydrogen. This review provides detailed information on the bioconversion processes and factors involved in hydrogen production from agro-industrial residues including different fermentation processes such as dark fermentation and photo-fermentation, and fuel cell systems such as microbial electrolysis cell and microbial fuel cell. Different pretreatment techniques to enhance the availability of lignocellulose for hydrogen production have been elaborated in this review. Various factors including pH, temperature and nutrient composition of feed, affecting the production efficiency and purity of the products during fermentation have been discussed.

We report CoFe2O4 nanoparticles (NPs) synthesized using a facile hydrothermal growth and their attachment on 3D carbon fiber papers (CFPs) for efficient and durable oxygen evolution reaction (OER). The CFPs covered with CoFe2O4 NPs show orders of magnitude higher OER performance than bare CFP due to high activity of CoFe2O4 NPs, leading to a small overpotential of 378 mV to get a current density of 10 mA/cm(2). Significantly, the CoFe2O4 NPs-on-CFP electrodes exhibit remarkably long stability evaluated by continuous cycling (over 15 h) and operation with a high current density at a fixed potential (over 40 h) without any morphological change and with preservation of all materials within the electrode. Furthermore, the CoFe2O4 NPs-on-CFP electrodes also exhibit hydrogen evolution reaction (HER) performance, which is considerably higher than that of bare CFP, acting as a bifunctional electrocatalyst. The achieved results show promising potential for efficient, cost-effective, and durable hydrogen generation at large scales using earth-abundant materials and cheap fabrication processes.

The objective of this work was to determine the hydrogen production from paper mill wastes using microbial consortia of solid substrate anaerobic digesters. Inocula from mesophilic, continuous solid substrate anaerobic digestion (SSAD) reactors were transferred to small lab scale, batch reactors. Milled paper (used as a surrogate paper waste) was added as substrate and acetylene or 2-bromoethanesulfonate (BES) was spiked for methanogenesis inhibition. In the first phase of experiments it was found that acetylene at 1% v/v in the headspace was as effective as BES in inhibiting methanogenic activity. Hydrogen gas accumulated in the headspace of the bottles, reaching a plateau. Similar final hydrogen concentrations were obtained for reactors spiked with acetylene and BES. In the second phase of tests the headspace of the batch reactors was flushed with nitrogen gas after the first plateau of hydrogen was reached, and subsequently incubated, with no further addition of inhibitor nor substrate. It was found that hydrogen production resumed and reached a second plateau, although somewhat lower than the first one. This procedure was repeated a third time and an additional amount of hydrogen was obtained. The plateaux and initial rates of hydrogen accumulation decreased in each subsequent incubation cycle. The total cumulative hydrogen harvested in the three cycles was much higher (approx. double) than in the first cycle alone. We coined this procedure as IV-SSAH (intermittently vented solid substrate anaerobic hydrogen generation). Our results point out to a feasible strategy for obtaining higher hydrogen yields from the fermentation of industrial solid wastes, and a possible combination of waste treatment processes consisting of a first stage IV-SSAH followed by a second SSAD stage. Useful products of this approach would be hydrogen, organic acids or methane, and anaerobic digestates that could be used as soil amenders after post-treatment.

The rate of production of molecular hydrogen upon illumination with solar radiation/visible light of immobilised CdS, ZnS and mixed CdS–ZnS on Whatman filter paper in Na2S/Na2SO3 solution have been studied. Enhancement of rate of hydrogen evolution has been observed by codeposited CdS with ZnS on Whatman filter paper. Mark enhancement in the rate of hydrogen liberation has been achieved by the catalyst at about 80 mol% Zn for a solid solution of Cadmium–Zinc sulphide embedded in Whatman filter paper.

Microbial electrolysis cells (MECs) are a new bio-electrochemical method for converting organic matter to hydrogen gas (H2). Palm oil mill effluent (POME) is hazardous wastewater that is mostly formed during the crude oil extraction process in the palm oil industry. In the present study, POME was used in the MEC system for hydrogen generation as a feasible treatment technology. To enhance biohydrogen generation from POME in the MEC, an empirical model was generated using response surface methodology (RSM). A central composite design (CCD) was utilized to perform twenty experimental runs of MEC given three important variables, namely incubation temperature, initial pH, and influent dilution rate. Experimental results from CCD showed that an average value of 1.16 m3 H2/m3 d for maximum hydrogen production rate (HPR) was produced. A second-order polynomial model was adjusted to the experimental results from CCD. The regression model showed that the quadratic term of all variables tested had a highly significant effect (P

Nickel nanoparticles (NiNPs) were successfully synthesized in situ on a microstructured paper matrix composed of inorganic fibers as the main framework and zinc oxide (ZnO) whiskers as a preferential support for NiNPs. The paper-like inorganic fiber/ZnO whisker composites were prepared using a high-speed and low-cost papermaking technique, and then simply immersed in an aqueous solution of Ni(NO3)2. After reduction in hydrogen flow, NiNPs with a fine size about 20 nm in diameter were selectively formed on the ZnO whiskers in the paper composites. As-prepared NiNPs@ZnO paper is much like an ordinary paper product, being flexible, lightweight, and easy to handle. The NiNPs@ZnO paper composites exhibited excellent catalytic performance in the steam reforming of propane, and produced hydrogen more efficiently than commercial pellet-type nickel catalysts. These results are possibly attributed both to highly active NiNPs synthesized in situ and to the uniform flow of reactants inside a microporous paper structure.

In situ synthesis of nickel/magnesium oxides (Ni/MgO) on a microstructured inorganic paper support was investigated to develop high-performance, easily handled, paper-like catalysts, using two different methods: sequential impregnation and co-impregnation approaches. Porous paper supports were prepared beforehand using a conventional papermaking technique, and then simply impregnated with Mg(NO 3 ) 2 and Ni(NO 3 ) 2 solutions, either stepwise or at the same time. After reduction in a hydrogen flow, Ni/MgO catalysts were formed in the paper composites. The as-prepared Ni/MgO paper is much like an ordinary paper product, being flexible, lightweight, and easy to handle. The Ni/MgO paper composites, especially the co-impregnated paper, exhibited excellent catalytic performances in the steam reforming of methane, and produced hydrogen much more efficiently than did commercial Ni-based catalysts in powdered and pellet forms. The Ni/MgO paper composites also showed good durability for 24-h continuous reaction, and maintained their initial efficiency for methane steam reforming. These results were attributed to the favorable supply of gaseous reactants to the active Ni/MgO catalysts, which were well distributed inside a microporous paper structure.

One-step multi-enzyme (OSME) pretreatment of Chlorella sp. biomass were statistically optimized. Enzyme dosages of 380 units/g-VS Termamyl SC, 229.45 units/g-VS Dextrozyme GA, and 34.13 filter paper units/g-VS Cellic CTec 2, and a hydrolysis time of 90 min were the optimal conditions yielding a RSY of 167.61 mg/g-VS, equivalent to 49.29% carbohydrate solubilization. An OSME pretreated biomass was used as substrate for biohydrogen production that was optimized under feed/inoculum ratio of 3.0 and initial pH of 6.5. A hydrogen yield of 43.16 mL-H2/g-VS was obtained under optimal conditions, which was 39.63% greater than that observed with non-treated biomass. Addition of nutrients in the form of a basic anaerobic medium with or without a nitrogen source, tended to decrease the efficiency of hydrogen production from the hydrolyzed biomass. This work demonstrated OSME hydrolysis as an alternative to the sequential hydrolysis processes for efficient conversion of microalgae biomass to fermentable sugars and biohydrogen.

The modernized world is over-consuming low-cost energy sources that strongly contributes to environmental stress. As a consequence, the interest for environmentally friendly alternatives has increased immensely. One such alternative is utilizing the diazotrophic nature of the heterocystous filamentous cyanobacteria Nostoc sp. as feedstock for biodiesel and hydrogen production using pulp and paper wastewater – a phosphorous and nitrogen deficient medium. In this work, biodiesel and hydrogen production was studied with respect to three main aspects: biodiesel quality properties, lipid content and hydrogen production coupled with a preliminary study investigating the luminous effects on the biomass and biodiesel quality properties when exposed to low (50 μEm-2s-1), medium (150 μEm-2s-1) and high light (300 μEm-2s- 1). The preliminary study showed that an increase of light intensity was associated with parabolic results for biomass following the 10-day cultivation period, with the medium light intensity showing an average dried weight of at the most 203% greater than the two other light intensities. When analysing the FAME- composition, similar results were demonstrated for the fatty acid constituents preferred for biofuel applications, C18:1 and C18:2 fatty acids, where the low, medium and high light showed an accumulative 34.65, 43.1 and 31.6 dwt % respectively. The strain could be of interest as feedstock for biodiesel when cultivated in pulp and paper wastewater, due to the positive results pertaining to the lipid content and biodiesel quality properties. Following the 10-day cultivation period the lipid content obtained was 35.9 dwt %. The biodiesel quality properties were tested to assess the strains suitability for biodiesel and were tested to ensure its accordance to the standards on commercial biodiesel quality; European Standard for Biodiesel as heating oil (EN 14213) and European Biodiesel Standard (EN 14214). The critical parameters tested were the regulated (iodine value, cetane number, density, viscosity, pour point, cold filter plugging point, oxidative stability) and unregulated (FAME-composition) fuel properties. Results obtained showed values within the regulated values set by the different standards. However, due to a high saturated fatty acid content, the strain showed inadequate low temperature flow properties (cloud point, pour point and the cold filter plugging point). This study shows that this strain has a low potential for hydrogen production, with a hydrogen production of 0.13 nmol/mg dry wt/h following the 10-day cultivation period. This low hydrogen production could be attributed to the among other things the current growth phase of the cyanobacteria. Chemical analyses were conducted for revealing the total nitrogen, total phosphorus and chemical oxygen demand (COD) content. Following the 10-day cultivation period, the samples showed a 22% decrease in phosphorous concentration, 11% decrease in COD concentration and 51% increase of nitrogen concentration. The probable causes for this increase is the Nostoc’s diazotrophic nature and the ammonium excretion nitrogen fixation entails, as well as the nitrogen release following the final algal growth phase – the death phase. In conclusion, the results showed great potential, however, further studies are recommended investigating the changes that occurs during cultivation period to further assess the strains potential as well as assessing the continuity of the results with a greater initial cellular concentration. Nonetheless, due to the positive results obtained regarding the nutrient uptake, biodiesel and hydrogen production, this study shows potential for further optimization for the use of Nostoc grown in pulp and paper wastewater for wastewater treatment, biodiesel and/or hydrogen production.

The generation of energy by thermoelectric plants powered by biomass in Brazil has grown by ∼3% in the last three years. In 2016, 8.8% of the electric energy in Brazil was generated using biomass as an input. However, the generation of residues and the possibility of reapproaching have motivated the planning and uses of electrochemical processes to evaluate the obtained gases (mainly hydrogen and carbon monoxide) as clean energy sources. Although thermochemical processes using biomass as an energy source already exist, few reports regarding the study of this process through electrolysis are available. Herein, we describe a water electrolysis process using sugarcane bagasse, rice husk, and malt bagasse as biomass residues to obtain gases with potential uses as clean energy sources and analyze the mass concentration influences on the behavior of the electrochemical solution. Tafel and cyclic voltammetry analyzes showed a tendency to decrease the kinetics and current of the system with the increase of the biomass residue concentration in the solution. In contrast, sugarcane bagasse concentrations of 0.1%–1% increase the current. The faradaic efficiency and partial current density analysis confirm the results obtained from cyclic voltammetry for hydrogen production, with less faradaic efficiency for hydrogen and reduced current values in the system when the biomass residue concentration is higher. The production efficiency of carbon monoxide formed at the anode increases with the concentration for sugarcane bagasse (2.01–5.21 μA/cm2) with 1% of the biomass in solution.

The present study demonstrates the feasibility of a two-phase biorefinery process applied to waste substrates producing ethanol rich effluents. The process includes a dark fermentation step followed by photo fermentation and it is able to optimize hydrogen production from waste biomass. The study was conducted using winery wastewater as feedstock. The results indicate that no additional treatments are required when an appropriate dilution of the initial waste is applied. Microbial consortia contained in the winery wastewater promoted a fermentative ethanol pathway. The ethanol rich effluent was converted into hydrogen by phototrophic microorganisms. Despite the presence of inhibiting compounds, the adoption of a mixed phototrophic culture allowed to obtain good results in terms of hydrogen production. Specifically, up to 310 mLH2 gCODconsumed−1 were obtained in the photo fermentative stage. The effectiveness of ethanol rich dark fermentation effluents for hydrogen production enhancement was demonstrated. Noteworthy, polyhydroxybutyrate was also produced during the experiments. The work faces two of the major challenges in the sequential dark fermentation and photo fermentation technology applied to real waste substrates: the minimization of pre-treatments and the enhancement of the hydrogen production yields using ethanol rich DFEs.

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.

A novel microstructured catalyst that consists of Cu/ZnO catalyst powders and ceramic fibers was successfully prepared using pulp fibers as a tentative matrix by a papermaking technique. As-prepared material, called a paper-structured catalyst, possessed porous microstructure with layered ceramic fiber networks (average pore size ca. 20 μm, porosity ca. 50%). In the process of methanol autothermal reforming (ATR) to produce hydrogen, paper-structured catalysts demonstrated both high methanol conversion and low concentration of undesirable carbon monoxide as compared with catalyst powders and pellets. The catalytic performance of paper-structured catalysts depended on the use of pulp fibers, which were added in the paper-forming process and finally removed by thermal treatment before ATR performance tests. Confocal laser scanning microscopy and mercury intrusion analysis suggested that the tentative pulp fiber matrix played a significant role in regulating the fiber-network microstructure inside paper composites. Various metallic filters with different average pore sizes, used as supports for Cu/ZnO catalysts, were subjected to ATR performance tests for elucidating the pore effects. The tests indicated that the pore sizes of catalyst support had critical effects on the catalytic efficiency: the maximum hydrogen production was achieved by metallic filters with an average pore size of 20 μm. These results suggested that the paper-specific microstructures contributed to form a suitable catalytic reaction environment, possibly by promoting efficient diffusion of heat and reactants. The paper-structured catalyst with a regular pore microstructure is expected to be a promising catalytic material to provide both practical utility and high efficiency in the catalytic gas-reforming process.

The developed Ni-La/Al2O3-CeO2-Bamboo charcoal (ACB) catalyst was applied to the co-pyrolysis of straw and plastic to produce hydrogen in a horizontal quartz tube pyrolysis furnace. In this study, the effects of the mixing ratio of straw and plastic, the presence and stability of the catalyst on the co-pyrolysis hydrogen production were investigated. Experiment showed that the addition of PE can increase the yield of H2 within a certain range, and the best mass ratio of 5:5 was found. In the co-pyrolysis process with the participation of the catalysts, the macromolecular tar can be cracked into combustible gases such as H2, and the H2 yield could be increased to 332.2ml/g (Ni-La/ACB) is much higher than 68.87ml/g without catalyst. Compared with Ni/ACB, Ni-La/ACB had been increased the alkalinity by adding La element and enhanced the carbon deposition resistance of the catalyst, which makes the catalyst maintain higher stability. This was also confirmed in stability test experiments.

Decreasing carbon dioxide (CO2) emission by converting to higher-valued product has become of interest. Hydrogen (H2) is an important feedstock required in thermochemical conversion of CO2 to chemicals such as methanol. The cost and availability of H2 affect the cost of CO2 conversion. This study is focused on the process simulation of H2 production from ethanol feedstock. Steam reforming of ethanol is compared with dehydrogenation of ethanol to H2 with valued products including ethyl acetate and acetaldehyde. Form this study, steam reforming of ethanol presents the lowest cost of H2 production at 1.58 USD/kg H2 while dehydrogenation of ethanol presents the cost at 3.24 and 1.97 USD/kg H2, respectively. Although presenting the lowest cost, steam reforming of ethanol provides a net positive CO2 emission in the overall CO2 conversion to methanol process. In contrast, ethanol dehydrogenation to H2 and byproducts, ethyl acetate and acetaldehyde, promotes a net negative CO2 emission of −819.20 kg/ton methanol and −5.42 kg/ton methanol, respectively. The results present a decreasing CO2 emission with an increasing cost of H2 production.

Copper-zinc oxide catalyst powders were successfully impregnated into paper-based composites (catalyst paper) of ceramic and silicon carbide (SiC) fibers, prepared using an established wet papermaking process. The catalyst powders were homogeneously scattered over the fiber-mix networks tailored within the catalyst paper. Samples of catalyst paper were subjected to the methanol steam reforming (MSR) process below 300 °C to produce hydrogen gas for fuel cell applications. During this process, the catalyst paper samples exhibited a higher methanol conversion efficiency and lower carbon monoxide concentration than those produced either by a commercial pellet-type Cu/ZnO catalyst or the original powdered Cu/ZnO catalyst. The high heat conductivity of the SiC fibers enhanced the catalytic performance, especially contributing to the suppression of the reverse water gas shift reaction. The heat transfer and the heat distribution inside the catalyst paper were improved by the SiC fibers. The MSR efficiency per catalyst weight was greatly influenced by the addition of pulp fibers, which made the catalyst paper porous. Results indicated that these in-paper void structures are suitable for the MSR reaction. Flexible catalyst paper is a promising, easy-to-handle material for practical MSR applications, due to the controllable heat and pore characteristics involved in the MSR performance.

Copper–zinc oxide catalyst powders were successfully prepared into paper-like composites, called catalyst paper in this study, using ceramic fibers as the carrier matrix of the catalyst. A papermaking technique with a dual polyelectrolyte retention system was used. Catalyst particles were supported on the ceramic fiber networks tailored in the catalyst paper having various types of pores. Pieces of catalyst paper were subjected to methanol steam reforming (MSR) to produce hydrogen gas for fuel cell applications. They demonstrated a higher performance for methanol conversion and hydrogen production in the MSR reaction than commercial Cu/ZnO catalyst pellets, exhibiting an efficacy equivalent to that of the original catalyst powders. The concentration of carbon monoxide, which acts as a catalytic poison for fuel electrode catalysts, decreased remarkably, without any carbon monoxide reduction system. Moreover, the porous structure of catalyst paper influenced the MSR efficiency. It was assumed that the macropores ca. 20 μm in diameter greatly contributed to the MSR performance, rather than the mesopores on the catalyst surfaces. Thus, the porous, flexible and easy-to-handle catalyst paper is a promising material for practical MSR applications.