Overcoming propionic acid inhibition of hydrogen fermentation by temperature shift strategy

A novel temperature shift strategy has been proposed to overcome an inhibition on hydrogen fermentation of beverage industry wastewater (BW) due to the accumulation of propionic acid (HPr) during continuous reactor operation. The continuous performance at constant pH 5.5, temperature 37 °C and hydraulic retention time (HRT) 8 h with BW concentration of 20 g/L_{hexose-equivalent} in a stirred tank reactor (2 L) showed an accumulation of HPr to 2.36 g/L leading to a drop in hydrogen production rate (HPR) from 10 to 8.5 L L⁻¹ d⁻¹. To overcome the HPr inhibition, a temperature shift (from 37 °C) to 45 °C for 8 h was applied. This significantly improved the inhibited HPR and HY to 13.6 L L⁻¹ d⁻¹ and 1.68 mol-H₂ mol⁻¹ hexose, respectively, with a simultaneous reduction in the HPr concentration to 0.7 g/L. Microbial community analysis based on PCR-DGGE after temperature shift revealed the non-dominance of Selenomonas lacticifex and Bifidobacterium catenulatum (involved in HPr formation), and dominance of hydrogen producing bacteria namely Clostridium butyricum, Clostridium perfringenes, Clostridium acetobutylicum, and Ethanoligenens harbinense. This study demonstrated that temperature shift strategy could overcome the HPr inhibition and significantly improve the hydrogen fermentation of an industrial wastewater.     

Purification and characterization of a highly thermostable, oxygen-resistant, respiratory [NiFe]-hydrogenase from a marine, aerobic hydrogen-oxidizing bacterium Hydrogenovibrio marinus

The membrane-bound [NiFe]-hydrogenase from Hydrogenovibrio marinus (HmMBH) was purified homogeneously under anaerobic conditions. Its molecular weight was estimated as 110 kDa, consisting of a heterodimeric structure of 66 kDa and 37 kDa subunits. The purified enzyme exhibited high activity in a wide temperature range: 185 U/mg at 30 °C and 615 U/mg at 85 °C (the optimum temperature). The K_m and k_cat/K_m values for H₂ were, respectively, 12 μM and 8.58 × 10⁷ M⁻¹ s⁻¹. The optimum reaction pH was 7.8, but its stability was particularly high at pH 4.0-7.0. Results show that HmMBH was remarkably thermostable and oxygen-resistant: its half-life was 75 h at 80 °C under H₂, and more than 72 h at 4 °C under air. The air-oxidized HmMBH for 72 h showed only weak EPR signals of Ni-B, suggesting a structural feature in which the active center is not easily oxidized.     

Effect of Ce on the structural features and catalytic properties of La(0.9−x)CexFeO3 perovskite-like catalysts for the high temperature water-gas shift reaction

La_(0.9−x)Ce_xFeO₃ perovskite-like catalysts were investigated for the production of hydrogen from simulated coal-derived syngas via the water-gas shift reaction in the temperature range 450-600 °C and at 1 atm. These catalysts exhibited higher activity at high temperatures (T ≥ 550 °C), compared to that of a commercial high temperature iron-chromium catalyst at 450 °C. Addition of a low Ce content (x = 0.2), has little influence on the formation of the LaFeO₃ perovskite structure, but enhances catalytic activity especially at high temperatures with 19.17% CO conversion at 550 °C and 40.37% CO conversion at 600 °C. The LaFeO₃ perovskite structure and CeO₂ redox properties play an important role in enhancing the water-gas shift activity. Addition of a high Ce content (x = 0.6) inhibits the formation of the LaFeO₃ perovskite structure and decreases catalyst activity.     

Dark fermentative hydrogen production from xylose by a hot spring enrichment culture

Dark fermentative hydrogen production by a hot spring culture was studied from different sugars in batch assays and from xylose in continuous stirred tank reactor (CSTR) with on-line pH control. Batch assays yielded hydrogen in following order: xylose > arabinose > ribose > glucose. The highest hydrogen yield in batch assays was 0.71 mol H₂/mol xylose. In CSTR the highest H₂ yield and production rate at 45 °C were 1.97 mol H₂/mol xylose and 7.3 mmol H₂/h/L, respectively, and at 37 °C, 1.18 mol H₂/mol xylose and 1.7 mmol H₂/h/L, respectively. At 45 °C, microbial community consisted of only two bacterial strains affiliated to Clostridium acetobutulyticum and Citrobacter freundii, whereas at 37 °C six Clostridial species were detected. In summary hydrogen yield by hot spring culture was higher with pentoses than hexoses. The highest H₂ production rate and yield and thus, the most efficient hydrogen producing bacteria were obtained at suboptimal temperature of 45 °C for both mesophiles and thermophiles.     

Parametric study on the pyrolysis of manure and wood shavings

In this work, a response surface methodology (RSM) was used to study the effects of temperature (A), feed rate (B) and gas flow rate (C) on the liquid yield, char yield and pH of the biocrude oil. Box-Behnken design was chosen and a total number of 15 experimental runs including 3 center runs were generated for the pyrolysis of a mixture of 50 wt.% layer manure and 50 wt.% loblolly pine wood shavings in a 50 mm bubbling fluidized bed reactor. The operational variables were as follows: temperature (400-550 °C), nitrogen gas flow rate (12-24 L/min), and feed rate (160-480 g/h). A second-order regression models were used to predict the responses. The analysis of variance (ANOVA) was performed with Minitab 16 software and the significant effect of the factors and their interaction effects were tested at 95% confidence interval. The biocrude yield was significantly influenced by temperature, feed rate and gas flow rate. Temperature was the only significant factor that influenced the char yield. Maximum biocrude yield (51.1 wt.%) was achieved at 475 °C with a feed rate of 480 g/h and a gas rate of 12 L/min. The lowest char yield (22.6 wt.%) was achieved at 550 °C, 320 g/h and 12 L/min and the biocrude had the highest pH (4.85) at 475 °C, 160 g/h and 24 L/min. The predictive models proposed agreed with the experimental values.     

Effect of changing temperature on anaerobic hydrogen production and microbial community composition in an open-mixed culture bioreactor

The temperature effect (37–65 °C) on H₂ production from glucose in an open-mixed culture bioreactor using an enrichment culture from a hot spring was studied. The dynamics of microbial communities was investigated by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). At 45 and 60 °C the H₂ production was the highest i.e. 1.71 and 0.85 mol H₂/mol glucose, respectively. No H₂ was produced at temperatures 50 and 55 °C. At 37–45 °C, H₂ production was produced by butyrate type fermentation while fermentation mechanism changed to ethanol type at 60 °C. Clostridium species were dominant at 37–45 °C while at 50–55 °C and 60 °C the culture was dominated by Bacillus coagulans and Thermoanaerobacterium, respectively. In the presence of B. Coagulans the metabolism was directed to lactate production. The results show that the mixed culture had two optima for H₂ production and that the microbial communities and metabolic patterns promptly changed according to changing temperatures.     

Constrained and unconstrained melting inside a sphere

The melting of the phase change material (PCM) inside a sphere using n-Octadecane for both constrained and unconstrained melting is investigated. In constrained melting, the solid PCM is restrained from sinking to the bottom of the sphere. For unconstrained melting, the solid PCM would sink to the bottom of sphere due to gravity. The experiments are carried out at three different wall temperatures of 35 °C, 40 °C and 45 °C with a sub-cooling of 1 °C for the unconstrained melting and three different initial sub-cooling of 1 °C, 10 °C and 20 °C at a constant wall temperature of 40 °C for the constrained melting.     

Galliosilicate glasses for viscous sealants in solid oxide fuel cell stacks: Part I: Compositional design

Galliosilicate glasses were developed for sealing intermediate temperature planar solid oxide fuel cell (SOFC) stacks. Candidate sealing glasses were identified for use at operating temperatures of 750 °C and at 850 °C after assessing flow behavior, thermal expansion properties, and crystallization behavior. A series of non-alkali glasses was identified for use at 750 °C within a strontium boro-galliosilicate compositional region that exhibited glass transition temperatures (T_g) between 658 and 675 °C and coefficients of thermal expansion (CTE) between 8 and 9.4 × 10⁻⁶ K⁻¹. Glass frits and powders flowed below 850 °C and did not crystallize dramatically after 500 h at 750 °C. Several glasses containing 5 mol% mixed alkali were identified in a strontium boro-galliosilicate compositional region for use at 850 °C. The glasses exhibited T_g between 615 and 620 °C with CTE from 7.8 to 9.7 × 10⁻⁶ K⁻¹. Glass frits flowed well below 850 °C and retained remnant glass phase after partial crystallization at 850 °C. The galliosilicate glasses developed in this work enable viscous sealing of SOFC stacks.     

Low temperature synthesis of Yb doped SrCeO3 powders by gel combustion process

In this work, SrCe_0.9Yb_0.1O_3−δ powders were synthesized by a gel combustion method which combined gel process and combustion process. The effect of ratio of citric acid to metal cations (C/M), oxidizer and calcination temperature on the properties of powders was investigated in detail. It was found that the extra oxidizer NH₄NO₃ increased the flame temperature of combustion and thus promoted the formation of SrCeO₃. The relative amount of SrCeO₃ in powder increased as the C/M ratio increased. The as-ignited powder at 250 °C mainly consisted of the perovskite SrCeO₃, i.e. relative amount of 95.2 wt%. The adiabatic flame temperature of the combustion reaction was calculated to be 1903.1 °C, higher than the required formation temperature of 787.2 °C for SrCeO₃. Furthermore, the pure perovskite phase powder with agglomerated microstructure and average grain size of 2 μm was obtained after calcination at 1200 °C for 5 h. This heat-treatment temperature is 200 °C lower than the conventional solid state reaction method for SrCe_0.9Yb_0.1O_3−δ preparation.     

Optimization of temperature and light intensity for improved photofermentative hydrogen production using Rhodobacter capsulatus DSM 1710

Photofermentative hydrogen production is influenced by several parameters, including feed composition, pH levels, temperature and light intensity. In this study, experimental results obtained from batch cultures of Rhodobacter capsulatus DSM 1710 were analyzed to locate the maximum levels for the rate and yield of hydrogen production with respect to temperature and light intensity. For this purpose, a 3^k general full factorial design was employed, using temperatures of 20, 30 and 38 °C and light intensities of 100, 200 and 340 W/m². ANOVA results confirmed that these two parameters significantly affect hydrogen production. Surface and contour plots of the regression models revealed a maximum hydrogen production rate of 0.566 mmol H₂/L/h at 27.5 °C and 287 W/m² and a maximum hydrogen yield of 0.326 mol H₂/mol substrate at 26.8 °C and 285 W/m². Validation experiments at the calculated optima supported these findings.     

Novel FISH and quantitative PCR protocols to monitor artificial consortia composed of different hydrogen-producing Clostridium spp.

The use of an artificial consortium composed of selected hydrogen-producing species, instead of a natural anaerobic sludge, has been proposed for biohydrogen production. In order to monitor such a consortium composed of different Clostridium spp., new protocols were tested for two different assays, FISH and qPCR. New species-specific FISH probes and qPCR primer sets were developed and optimised for three strains: Clostridium butyricum, Clostridium felsineum and Clostridium pasteurianum, that were used in a consortium. Application of a fast two-step FISH protocol, with pre-treatment step at 90 °C for 5 min and a subsequent hybridisation step at higher temperature (55 °C) for 20 min resulted in a much shorter analytical time compared to the standard FISH procedure (46 °C for 2-3 h) and gave a high hybridisation performance. Moreover, to accurately quantify each microorganism by qPCR assay, two innovations were tested: the direct use of cell lysates (omitting the DNA extraction step) and the use of two alternative molecular markers, recA and gyrA. These markers are present in single copies in the genome, whereas there are multiple copies of the ribosomal operons. This resulted in the development of accurate, reliable and fast FISH and qPCR assays for routine monitoring of the dynamics of artificial hydrogen-producing microbial consortia. Moreover, both techniques can be easily adapted to new Clostridium strains.     

Nanostructured cadmium oxide thin films for hydrogen sensor

Cadmium oxide (CdO) thin films have been deposited by reactive dc magnetron sputtering on to glass substrates at room temperature and subsequently annealed at 275 °C for 3 h in vacuum. The as-deposited and annealed films were characterized for their structural and optical properties. The films were also tested for hydrogen sensing at different operating temperatures. The annealed samples showed better response down to 50 ppm at a relatively low operating temperature of 100 °C. The role of non-equilibrium surface states as a possible sensing mechanism is explained.     

Isothermal torrefaction kinetics of hemicellulose, cellulose, lignin and xylan using thermogravimetric analysis

In recent years, torrefaction, a mild pyrolysis process carried out at the temperature range of 200-300 °C, has been considered as an effective route for improving the properties of biomass. Hemicellulose, cellulose, lignin and xylan are the basic constituents in biomass and their thermal behavior is highly related to biomass degradation in a high-temperature environment. In order to provide a useful insight into biomass torrefaction, this study develops the isothermal kinetics to predict the thermal decompositions of hemicellulose, cellulose, lignin and xylan. A thermogravimetry is used to perform torrefaction and five torrefaction temperatures of 200, 225, 250, 275 and 300 °C with 1 h heating duration are taken into account. From the analyses, the recommended values of the order of reaction of hemicellulose, cellulose, lignin and xylan are 3, 1, 1 and 9, respectively, whereas their activation energies are 187.06, 124.42, 37.58 and 67.83 kJ mol⁻¹, respectively. A comparison between the predictions and the experiments suggests that the developed model can provide a good evaluation on the thermal degradations of the constituents, expect for cellulose at 300 °C and hemicellulose at 275 °C. Eventually, co-torrefaction of hemicellulose, cellulose and lignin based on the model is predicted and compared to the thermogravimetric analysis.     

Dilute oxalic acid pretreatment for biorefining giant reed (Arundo donax L.)

Biomass pretreatment is essential to overcome recalcitrance of lignocellulose for ethanol production. In the present study we pretreated giant reed (Arundo donax L.), a perennial, rhizomatous lignocellulosic grass with dilute oxalic acid. The effects of temperature (170-190 °C), acid loading (2-10% w/w) and reaction time (15-40 min) were handled as a single parameter, combined severity. We explored the change in hemicellulose, cellulose and lignin composition following pretreatment and glucan conversion after enzymatic hydrolysis of the solid residue. Two different yeast strains, Scheffersomyces (Pichia) stipitis CBS 6054, which is a native xylose and cellobiose fermenter, and Saccharomyces carlsbergensis FPL-450, which does not ferment xylose or cellobiose, were used along with commercial cellulolytic enzymes in simultaneous saccharification and fermentation (SSF). S. carlsbergensis attained a maximum ethanol concentration of 15.9 g/l after 48 h at pH 5.0, while S. stipitis, at the same condition, took 96 h to reach a similar ethanol value; increasing the pH to 6.0 reduced the S. stipitis lag phase and attained 18.0 g/l of ethanol within 72 h.     

Effect of a mild torrefaction for production of eucalypt wood briquettes under different compression pressures

The heat treatment of wood (i.e. torrefaction) followed by densification of wood particles (e.g. by briquetting) may be used as a process to improve homogeneity and energy properties of wood for use as a solid fuel. The wood of Eucalyptus grandis and Eucalyptus spp. were treated at 180, 200 and 220 °C for 60 min under a nitrogen atmosphere. Briquettes were produced with untreated and heat-treated wood particles using 120 °C, for 7 min pressing and 6 min cooling time, under pressures of 6.9, 10.3 and 13.8 MPa. The briquetting compacting pressure showed no significant influence on the briquettes properties. Briquettes density was similar for all cases presenting 1.14 g cm⁻³ for Eucalyptus spp. and 1.06 g cm⁻³ for Eucalyptus grandis wood. A mild torrefaction of the wood at 200–220 °C increased the potential energy of the particles and briquettes, showing an improvement in their density, dimensional stability and hygroscopicity. Briquettes produced from heat-treated Eucalyptus spp. wood presented higher energy density (24.79 GJ m⁻³) at 200°C-treatment when compared with untreated wood (20.76 GJ m⁻³). Regarding E. grandis, briquettes produced with heat-treated (200 °C) particles showed only a marginal higher energy content than with untreated wood, 21.70 GJ m⁻³ and 21.38 GJ m⁻³, respectively. The two eucalypt woods showed differences regarding the heat treatment and briquetting, pointing out that the optimization of these processes should be specific for each species. However, a mild torrefaction of the wood particles decreased the differences between materials which might be useful as a process to increase feedstock homogeneity when using mixed raw-materials.     

Structural characteristics of nanoparticles produced by hydrothermal pretreatment of cellulose and their applications for electrochemical hydrogen generation

Hydrothermal pretreatment (HTP) of microcrystalline cellulose (MCC) and wood sawdust in water at 200 °C and 250 °C and at pressures up to about 600 psi for different heating times (≤60 min) is shown to produce nanoparticles of about 210 nm diameter. For the shorter treatment times of 15 min, only partial conversion is observed. Investigations of the post-HTP solid products by scanning electron microscopy show that the original size of cellulose particles is reduced by a factor of about 50 to yield spherical nanoparticles of about 210 nm size. In X-ray diffraction studies, the characteristic Bragg peaks of the parent MCC and sawdust are not present in the post-HTP products with only a broad halo being observed, indicating that the crystallinity of cellulose has broken down under HTP. Electron spin resonance (ESR) spectroscopy shows the observation of free radicals in the post-HTP products whereas the parent MCC, sawdust and glucose are ESR inert. FTIR spectroscopy shows the breakdown of the bonds between glucose units of the cellulosic structure. As an application, the pre- and post-HTP cellulose and sawdust were tested for the electrochemical production of hydrogen. Whereas the pre-HTP samples were found to be inactive, the post-HTP cellulose treated at 250 °C for 60 min was nearly as active as carbon BP2000 (surface area = 1500 m²/g) for producing H₂ at energy efficient voltages. A comparative energy analysis for the electrochemical production of hydrogen using carbons and post-HTP cellulose vis-a-vis water electrolysis is also presented.     

Electrochemical performance of La2Cu1−xCoxO4 cathode materials for intermediate-temperature SOFCs

K₂NiF₄-type structure oxides La₂Cu_1−xCo_xO₄ (x = 0.1, 0.2, 0.3) are synthesized and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). The materials are characterized by XRD, SEM and electrochemical impedance spectrum (EIS), respectively. The results show that no reaction occurs between La₂Cu_1−xCo_xO₄ electrode and Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte at 1000 °C. The electrode forms good contact with the electrolyte after sintering at 800 °C for 4 h in air. The electrode properties of La₂Cu_1−xCo_xO₄ are studied under various temperatures and oxygen partial pressures. The optimum composition of La₂Cu_0.8Co_0.2O₄ results in 0.51 Ω cm² polarization resistance (R_p) at 700 °C in air. The rate limiting step for oxygen reduction reaction (ORR) is the charge transfer process. La₂Cu_0.8Co_0.2O₄ cathode exhibits the lowest overpotential of about 50 mV at a current density of 48 mA cm⁻² at 700 °C in air.     

Investigation of grain boundary formation in PtRu/C catalyst obtained in a polyol process with post-treatment

The grain boundary formation in PtRu/C catalyst obtained in a polyol process with post-treatment was investigated by scanning transmission electron microscopy, transmission electron microscopy (TEM) and High resolution TEM. The crystalline structure and surface composition of the PtRu/C catalysts were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical activities were evaluated by CO stripping voltammetry and linear sweep voltammetry measurements in combination with in situ IR reflection-absorption spectroscopy. As-prepared isolated spherical nanoparticles on the carbon support started to interconnect after washing procedure, and the interconnection between the particles was greatly promoted by reduction post-treatment at 80 °C; grain boundary formation occurred in the interconnected particles with increasing reduction temperature to 200 °C, and the particles reconstructed severely with further increasing reduction temperature to 400 °C. The defects at the grain boundary served as active sites for methanol electro-oxidation by weakening CO_ads adsorption on Pt sites and facilitating OH_ads formation, and the PtRu/C catalyst treated in 5% H₂/Ar at 200 °C for 10 h had the greatest catalytic activity for methanol electro-oxidation among the PtRu/C catalysts treated under various atmospheres and temperatures.     

LaCo0.6Ni0.4O3−δ as cathode contact material for intermediate temperature solid oxide fuel cells

LaCo_0.6Ni_0.4O_3−δ (LCN64) was prepared through the polymeric steric entrapment precursor route with Polyvinyl alcohol (PVA) as the entrapment agent and was evaluated as a contact material between the metallic interconnect and the cathode in planar intermediate temperature solid oxide fuel cell stacks (IT-SOFC). The ratio of PVA to metal nitrates and the calcination temperature of the precursor were optimized for the process. The electrical conductivity and thermal expansion coefficient (TEC) of the synthesized LCN64 and its chemical compatibility with SUS 430 were also characterized. The results indicate that 1:4 is a proper ratio of PVA to metal nitrates for process control and safety management; and calcination of the precursor at temperatures above 650 °C leads to formation of single perovskite phase LCN64. The conductivity of fully sintered LCN64 is above 1150 S cm⁻¹ in the temperature range between 100 °C and 800 °C, which is higher than those of conventional contact materials La_1−xSr_xMnO₃ (LSM) and LaNi_yFe_1−yO₃ (LNF). The average TEC is 17.22 × 10⁻⁶ K⁻¹ at temperatures below 900 °C, which is higher than those of the metallic interconnect and cell components. Mn and Cr elements contained in SUS 430 migrated into the porous LCN64 layer at 800 °C without chemically forming resistive phases.     

Optimization of two-stage fractionation process for lignocellulosic biomass using response surface methodology (RSM)

A two-stage process using aqueous ammonia and hot-water has been investigated to fractionate corn stover. To maximize hemicelluloses recovery and purity in the liquid hydrolyzate by optimizing the fractionation process, the experiments were carried out employing response surface methodology (RSM). A central composite design (CCD) was used to evaluate and confirm the effectiveness and interactions of factors. The optimal fractionation conditions were determined to be as follow: (1) First-stage reactor operated in batch mode using a 15% NH₄OH solution (w_NH3 = 15%) at 1:10 solid:liquid ratio, 60 °C, and 24 h; (2) second stage percolation reactor operated using hot-water at 20 cm³ min⁻¹, 200 °C, and 10 min.The model predicted 51.5% xylan recovery yield and 82.4% xylan purity under these conditions. Experiments confirmed the maximum xylan recovery yield and purity were 54.7% and 83.9% respectively under the optimal reaction conditions.With the solids resulting from the two-stage treatment, 87%-98% glucan digestibilities were obtained with 15 FPU of GC 220 per g-glucan and 30 CBU of Novo 188 per g-glucan enzyme loadings. Xylan digestibility of xylooligomer hydrolysates reached 76% with 8000 GXU per g-xylan of Multifect-Xylanase loading. In the simultaneous saccharification and fermentation (SSF) test using treated solids and Saccharomyces cerevisiae (D₅A), 86 % to 98% of ethanol yield was obtained on the basis of the glucan content in the treated solids.