Control strategies for biohydrogen production by immobilized co-culture of Clostridium butyricum and Rhodopseudomonas palustris

In this study, we evaluated biohydrogen production of Clostridium butyricum and Rhodopseudomonas palustris by immobilized co-culture. Effects of free cells and immobilized cells, immobilized biomass ratio, sucrose concentration, and initial pH on hydrogen production were investigated. The immobilized co-culture can achieve high cumulative hydrogen volume yield (604 mL) as compared to free co-culture cumulative hydrogen volume (513 mL) while the initial sucrose concentration was 17.8 g/L. The optimum C. butyricum/R. palustris ratio was 1:10, yielding the highest cumulative hydrogen (728 mL). High sucrose concentration (above 35.6 g/L) would inhibit hydrogen production. The optimal initial pH value for hydrogen production of immobilized co-culture was 7.0 (cumulative hydrogen volume 830 mL).     

Optimization of pretreatment conditions for enhanced sugar release

Present investigation was done to evaluate various algal genera found in water bodies of Varanasi city. The potential of any biomass for biofuels (bioalcohols, biohydrogen, etc.) production depends on the quantity of extractable sugar present in it. Acid (H₂SO₄) and alkali (NaOH) pretreatment were performed, and H₂SO₄ was chosen due to its nearly double yield as compared with alkaline pretreatment. Response surface methodology was utilized for the optimization of operating parameters such as treatment temperature, time, and acid concentration. Sugar yield up to 0.33 g/g of dry biomass was obtained using cyanobacterial biomass of Lyngbya limnetica, at 100°C, 59.19 min, and H₂SO₄ concentration of 1.63 M.     

Heterostructure CdS/ZnS nanoparticles as a visible light-driven photocatalyst for hydrogen generation from water

(CdS)_x/(ZnS)_1–x nanoparticles were synthesized as a visible light-driven photocatalyst using the stepped microemulsion technique with a series of the ratio factors (x). The photocatalytic test results showed that (CdS)_x/(ZnS)_1-x with x = 0.8 had the highest photo-reactivity for H₂ production from water under visible light. The composite (CdS)_0.8/(ZnS)_0.2 catalyst had a heterogeneous structure that exhibited a much greater photocatalytic hydrogen production activity than either pure CdS or the homogeneous Cd_0.8Zn_0.2S solid solution. ZnS deposition also was shown to largely improve the stability of CdS in the heterostructured CdS/ZnS catalyst. Thermal treatment of the catalyst, i.e., annealing (CdS)_0.8/(ZnS)_0.2 at 723 K, improved the crystallinity of the catalyst and increased its photocatalytic H₂ production rate by more than 36 times. Deposition of Ru on the surface of the catalyst particles by in situ photo-deposition further increased the photo-H₂ generation rate by 3 times. The photocatalyst of 0.5%Ru/CdS/ZnS achieved the highest H₂ production activity, at a rate of 12650 μmol/g-h and with a light to hydrogen energy conversion efficiency of 6.5%.     

Optimal Absorbent Evaluation for the CO2 Separating Process by Absorption Loading,Desorption Efficiency,Cost, and Environmental Tolerance

The CO₂ absorption capacities of potassium glycinate, potassium sarcosinate (choline, proline), mono-ethanolamine (MEA), and tri-ethanolamine were evaluated to find the optimal absorbent for separating CO₂ from gaseous products by a CO₂ purification process. The absorption loading, desorption efficiency, cost, and environmental tolerance were assessed to select the optimal absorbent. MEA was found to be the optimum absorbent for separating the CO₂ and H₂ mixture in gaseous product. The maximum absorption loading rate was 0.77 mol CO₂ per mol MEA at temperature of 20°C and absorbent concentration of 2.5 mol/L, whereas desorption efficiency was 90% by heating for 3 h at 130°C. MEA was found to be an optimal absorbent for the purification process of CO₂ during gaseous production.     

Relationship between liquid depth and the acoustic generation of hydrogen: design aspect for large cavitational reactors with special focus on the role of the wave attenuation

Understanding the effect of the liquid depth (z) on the acoustic generation of hydrogen is highly required for designing large-scale sonoreactors for hydrogen production because acoustic cavitation is the central event that initiates sonochemical reactions. In this paper, we present a computational analysis of the liquid-depth effect on the generation of H₂ from a reactive acoustic bubble trapped in water irradiated with an attenuating sinusoidal ultrasound wave. The computations were made for different operating conditions of frequency (355–1000 kHz), acoustic intensity (1–5 W/cm²), and liquid temperature (10–30°C). The contribution of the acoustic wave attenuation on the overall effect of depth was appreciated for the different conditions. It was found that the acoustic generation of hydrogen diminished hardly with increasing depth up to z = 8 m, and the depth effect was strongly operating parameter-dependent. The sound wave attenuation played a crucial role in quenching H₂ yield, particularly at higher z. The reduction of the H₂ yield with depth was more pronounced at higher frequency (1000 kHz) and lower temperature (10°C) and acoustic intensity (1 W/cm²). The attenuation of the sound wave may contribute up to 100% in the overall reductive effect of depth toward H₂ production rate. This parameter could be imperatively included when studying all aspects of underwater acoustic cavitation.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Techno-economic study of CO2 capture from natural gas based hydrogen plants

Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas (SMR). The future expansion of oil sands operations is likely to quadruple the demand of H₂ for oil sand operations in the next decade.This paper presents modified process schemes that capture CO₂ at minimum energy penalty in modern SMR plants. The approach is to simulate a base case H₂ plant without CO₂ capture and then look for the best operating conditions that minimize the energy penalty associated with CO₂ capture while maximizing H₂ production. The two CO₂ capture schemes evaluated in this study include a membrane separation process and the monoethanolamine (MEA) absorption process. A low energy penalty is observed when there is lower CO₂ production and higher steam production. The process simulation results show that the H₂ plant with CO₂ capture has to be operated at lower steam to carbon ratio (S/C), higher inlet temperature of the SMR and lower inlet temperatures for the water gas-shift (WGS) converters to attain lowest energy penalty. Also it is observed that both CO₂ capture processes, the membrane process and the MEA absorption process, are comparable in terms of energy penalty and CO₂ avoided when both are operated at conditions where lowest energy penalty exists.     

Demonstration of a high throughput on-board hydrogen generation reactor system using aluminum coil as fuel for a vehicle

A novel on-board hydrogen generation concept using Al coil with NaOH was investigated. The reaction rate was successfully controlled by introducing a pumping system for the NaOH solution. The time for the flow to develop fully was mainly dependent on the solution temperature, and the fastest start time recorded was 60 sec at a solution temperature of 70°C. The maximum H₂ generation rate was 200 L min^–1 with a prototype design of the on-board hydrogen generation system 1/8 times the size of a full-size reactor. The H₂ generation process coupled with the solution pumping system was simulated with three-dimensional fluid dynamic software, and the calculated H₂ flow and temperature rise of the system were validated with experimental data.     

Comparison of different pre-treatment methods for enriching hydrogen-producing bacteria from intertidal sludge

Batch tests of cultivations were conducted to analyze influences of pre-treatment methods (heat–shock, acid, and alkaline) on hydrogen production. The hydrogen yields of the pre-treated samples were significantly higher than those without pre-treatment. Heat–shock pre-treatment yielded maximum hydrogen (75.5 ± 4.0 mL/g sucrose_removed), and had the highest sucrose removal efficiency (81.20 ± 1.23%). Heat–shock pre-treatment produced more ethanol and acetate (80.44 ± 0.55% of the total soluble metabolites), which belonged to ethanol-type fermentation. Denaturing gradient gel electrophoresis (DGGE) profiles showed that pre-treatment methods affected the composition of microbial communities. The results showed that pre-treatment methods play a key role in the hydrogen production process of marine hydrogen-producing microflora.     

Gasification of Inferior Coal with High Ash Content under CO2 and O2/H2O Atmospheres

The gasification reaction of Nantong inferior coal was investigated in a laboratory fixed-bed reactor under CO₂ and O₂/H₂O atmospheres. The effects of the bed temperature and inlet-gas concentration on the yields of CO, H₂, and CH₄ were studied. The effects of coal ash and particle size on the fixed-carbon conversion were also investigated, and kinetic analysis was conducted with a homogeneous model. The product-gas-heating value and fixed-carbon conversion increased when the temperature was increased from 950 °C to 1100 °C under CO₂ atmosphere. When the inlet-CO₂ concentration was increased from 50 to 100 vol.%, the low heating value of the product gas and carbon conversion ratio slightly increased. During the gasification of inferior coal under the O₂/H₂O atmosphere, the CO concentration increased rapidly with increasing temperature. The H₂ and CH₄ concentrations increased initially and then decreased. The maximum gas heating value of 7934 kJ/m³ was obtained under the O₂ concentration of 70 vol.% at a bed temperature of 1050 °C. The cold-gas efficiency increased with increasing temperature and became 40.6% and 86.4% at 1100 °C under the CO₂ and O₂/H₂O atmospheres, respectively. The gasification reaction of the Nantong inferior coal strongly depended on the content of inherent inorganic matter. The gasification rates for both the CO₂ and O₂/H₂O atmospheres were independent of the particle size. The activation energy for the CO₂ and O₂/H₂O gasification reactions were 137 and 81 kJ/mol, respectively. The gasification reactions of the Nantong coal, which was performed under two different atmospheres, were compared and the reaction activity of the gasification reaction under CO₂ atmosphere was found to be much lower than that under the O₂/H₂O atmosphere.     

Parametric analysis of water electrolysis by dual electrolytes and cells

In this study, sulfuric acid and potassium hydroxide are used as the electrolytes, separated by proton exchange membrane, to produce hydrogen. The effects of electrolyte concentrations, applied voltage, single or dual cells, and temperature on the hydrogen production rate and energy efficiency are investigated. Experimental results show that the amount of hydrogen production increases with voltage, and the dual electrolytes and cells can yield the best hydrogen production rate and energy efficiency. With 1-M KOH plus 1-M H₂SO₄ as electrolytes in separated cells, the highest hydrogen production rate is about 0.95 L/hr. Results also show that the rise of electrolyte temperature can significantly increase the hydrogen production rate up to 50%, and the energy efficiency up to 20%. Keeping a low PH value in cathodeand high anode PH value in anode indeed enhances the efficiency of hydrogen production rate.     

A Thermodynamic View of Partial Oxidation,Steam Reforming,and Autothermal Reforming on Methane

Abstract

Thermodynamic analysis on three thermo-chemical reforming processes, i.e., partial oxidation (POX), steam reforming (STR), and autothermal reforming (ATR) with methane as the feedstock fuel are conducted in this study. The focus of this article is to show the effect of air-fuel (AF) ratio, water-fuel (WF) ratio, temperature and pressure on hydrogen (H₂) yield, hydrogen/carbon monoxide (H₂/CO) ratio, carbon (C), and carbon monoxide (CO) formation. Optimal operating conditions under no solid carbon formation in the reaction are recommended for each thermochemical reforming technique.     

Validation of a dynamic model of hydrogen permeation through Pd-based membranes

Pd-based membranes have been studied for pure hydrogen separation from syngas: in particular, a mathematical model of a Pd membrane for hydrogen separation has been developed.This model can be used in process and assessment studies of the parameters which characterize the mass transfer phenomena (such as: hydrogen permeability, surface coverage and limiting step). By coupling the permeation and water gas shift reaction kinetics, it can also be used to evaluate the performances of the membrane reactor. Further, it can be helpful to evaluate the best assembly and sizing of a H₂/CO₂ separation system.The model takes into account the kinetics of H₂ adsorption/desorption on Pd surface, the H₂ permeation into the palladium bulk and in the porous layer, and the kinetics of CO, CO₂, H₂O, O₂, H₂S competitive adsorption/desorption on Pd surface. It is also comprehensive of flux equations and bulk mass, momentum and energy balance.The results released by the model were compared to the experimental data during both the transient phase and the steady state conditions. A satisfactory agreement between model and experimental data was found.     

Biohythane production from pineapple peel using Methanosarcina mazei enhanced with palm oil mill effluent (POME) sludge in single-stage anaerobic digestion

Biohythane production via single-stage anaerobic digestion (AD) is an effective way for sustainable energy recovery from lignocellulosic biomass. In this paper, biohythane was produced through the AD process from pineapple peel waste substrate using purely cultured Methanosarcina mazei with the enhancement of palm oil mill effluent (POME) sludge as the inoculum. This study focuses on the effects of the lignocellulosic pre-treatment method, the addition of POME sludge into M. mazei culture medium as inoculum, and various operational conditions (food to microorganisms (F/M) ratios, temperature, pH) on gas production performances. The experimental results indicate that these parameters influenced the efficiency of biohythane production by producing the peak maximum biohythane production rate values (HPR_max) and (MPR_max), H₂:CH₄ = 1.93:0.67 L/L-d, and biohythane yield (HY) and (MY), H₂:CH₄ = 1.18:0.55 mL/L-substrate. This study demonstrates that biohythane gas (H₂ + CH₄ + CO₂) production from pineapple waste can be accelerated by M. mazei only with the enhancement of POME sludge through single-stage AD system under mesophilic batch process conditions.     

Mineralization of integrated gasification combined-cycle power-station wastewater effluent by a photo-fenton process

The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H₂O₂ and air to the system.The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H₂O₂ flow rate = 120 mL/h, [Fe(II)] = 7.6 mg/L, pH = 3.75 and air flow rate = 1 m³/h), a 90% mineralization was achieved in 150 min.Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H₂O₂ was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H₂O₂ was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process.Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.     

Phosphorus-doped graphene supported palladium (Pd/PG) electrocatalyst for the hydrogen evolution reaction in PEM water electrolysis

PEM water electrolysis is one of the most efficient methods for the production of hydrogen because of produced high purity of the gases and environmentally friendly. In the present study, Phosphorus-doped Graphene (PG) was synthesized by thermal annealing of triphenylphosphine (TPP) and graphene oxide (GO). The PG supported palladium (Pd/PG) electrocatalysts were synthesized by chemical reduction method and used as the cathode for hydrogen evolution reaction (HER) electrode. Structural properties and electrochemical performances of the synthesized Pd/PG electrocatalyst were studied by FE-SEM, EDS, ICP, FT-IR, XRD, and Cyclic voltammetry (CV) methods, respectively. The membrane electrode assemblies (MEA’s) were fabricated using Pd/PG as cathode for HER electrode and RuO₂ as anode for OER electrode. Also, their electrochemical performances along with the corresponding hydrogen yields were evaluated in single cell PEM water electrolyzer at various experimental conditions such as different current densities from 0.1 to 2.0 A cm^?2 and temperatures (28–80°C). The synthesized Pd/PG electrocatalyst was observed a current density of 1 A cm^?2 with 1.95 V at 80°C. Further, long-term stability studies were carried out continuously up to 2000 h which showed a reasonable stability. Hence, the synthesized Pd/PG can be used as an alternative to Pt-based electrocatalysts for the HER in PEM water electrolysis.     

Synthesis and characterization of multi-walled carbon nanotubes from silkworm cocoons to use as the cathode material for Al-air battery

ABSTRACT

Carbon nanotubes have been synthesized by chemical vapor deposition at 850°C using silkworm cocoons as a precursor. The impregnation method with 3 wt% ferrocene as a catalyst was utilized for growth of carbon nanotubes. The flow rates of C₂H₂, H₂, and N₂ were fixed at 100, 150, and 350 ml/min, respectively. Morphology, microstructure and quality of the synthesized carbon nanotubes were investigated by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy techniques. Results showed that the prepared carbon nanotubes were multiwalled and good graphitic quality. When used as the cathode material for aluminum-air battery, prepared carbon nanotubes cathode exhibited higher current density than commercial graphite cathode. Based on our study, there is a successful conversion of silkworm cocoons into value-added nanomaterial products, promoting the natural biotechnological materials.     

Improving the Synthesis Gas Quality in Catalytic Gasification of Rice Straw by an Integrated Hot-Gas Cleaning System

This research investigates an enhanced removal rate of tar and trace pollutants (e.g. hydrogen chloride and hydrogen sulfide, H₂S) in the gasification of rice straw, using an integrated in situ tar reduction and hot-gas cleaning technique. The gasification temperature was set at 900°C and equilibrium ratio (ER) was 0.30 in the gasifier. In the in situ tar reduction method, the catalyst, dolomite with an amended ratio of 0–15% was introduced to the gasifier. The integrated hot-gas cleaning system applied a multi-packed tower to remove the tar, sulfur and/or chlorine byproduct in syngas at 250°C. The packed materials composed of zeolite, calcined dolomite and activated carbon. The experimental results indicated that the tar concentration of syngas was approximately 20 g/kg. However, in catalytic gasification with 5% dolomite addition, the tar concentration reduced to 17 g/kg. The tar reduction efficiency was approximately 15% by an in situ dolomite addition. When applying the integrated hot-gas cleanup system, the tar was virtually eliminated. The total tar elimination rate was almost 100% and the cleaned syngas could be applied in other energy utilization equipment. On the other hand, the H₂S and HCl concentration were 101 ppmv and 991 ppmv, respectively. After the integrated syngas cleaning system, the H₂S and HCl were decreased to 7.9 ppmv and 410 ppmv with a removal efficiency of 92.1% and 58.6%, respectively. It can be concluded that combining the in situ method with the integrated syngas cleaning system can effectively reduce the amount of byproduct and enhance the syngas quality in the gasification of rice straw.     

Biomass from phytopathogens and culture conditions improve Penicillium chrysogenum antimicrobial activity and antifungal compounds production

The present study evaluated the effect of culture conditions and phytopathogenic strain co-culture on the production of antimicrobial metabolites and antifungal activity of Penicillium chrysogenum R1, which PCR identified. Antimicrobial activity was determined using the Hunter-Hunter experimental design with three factors (pH, incubation temperature, and inoculum, at two levels each). The antifungal metabolites, β 1-3 glucanase and chitinase, produced in the presence of live and inactivated Fusarium oxysporum Fsox C11 biomass, were evaluated using HPLC-MS and GC-MS. Results showed that P. chrysogenum inhibited the growth of five phytopathogenic fungal strains, and the most significant inhibition was observed for F. oxysporum Fsox C11. The best conditions to achieve the highest antifungal activity of the cell-free extract were pH 7, 28°C, 1 × 10⁶ spores/mL, and 144 h of fermentation, observing 86% inhibition of F. oxysporum Fsox C11 growth. Production of antifungal metabolites such as 1,4-benzoquinone imine, viridicatic acid, phenol-5-methyl-2-(1-methyl ethyl), and hydrolytic enzymes β 1-3 glucanase and chitinase was detected. The results define the perspective in designing new processes and products for biocontrol phytopathogens.     

Renewable biofuel production from hydrocracking of soybean biodiesel with a commercial petroleum Ni-W catalyst

As a potential hydrocarbon production method, the hydrocracking of soybean biodiesel, using a commercial petroleum hydrocracking catalyst, was studied. Experiments were carried out in a 1,000 mL, high-pressure autoclave for 2–4 hr over the temperature range of 200–280°C under an initial hydrogen pressure of 10 MPa. Hydrocracking of soybean biodiesel produced n-paraffins in the C₈–C₁₇ boiling range, which includes both green gasoline and diesel. Both pressure and temperature play important roles in the transformation of soybean biodiesel. Hydrocarbons can be formed above 220°C with a liquid yield of 81.76%. The n-alkanes content of the liquid product reached 32.29% at 280°C, with 88.32% C₁₁–C₁₄ selectivity. In addition, hydrocracking results in many changes of catalyst such as physical properties, morphology, etc. For the used catalyst, the concentrations of Ni and C increased, and the pore channels were significantly reduced.