Biogas upgrade to syn-gas (H2-CO) via dry and oxidative reforming

Fuel reforming processes are primarily used to generate hydrogen for fuel cells and in automotive internal combustion engines to improve combustion characteristics and emissions. In this study, biogas is used as the fuel source for the reforming process as it has desirable properties of being both renewable and clean. Two reforming processes (dry reforming and combined dry/oxidative reforming) are studied. Both processes are affected by the gas stream temperature and reactor space velocity with the second process being affected by O₂/CH₄ ratio as well. Our results imply that oxidative reforming is the dominant process at low exhaust temperatures. This provides heat for the dry reforming of biogas and the overall reforming is exothermic. Increase in O₂/CH₄ ratio at low temperature promotes hydrogen production. At high exhaust temperatures (>600 °C), dry reforming of biogas is dominant and the overall reaction is net endothermic.     

Design of CO2 absorption plant for recovery of CO2 from flue gases of gas turbine

The ongoing human-induced emission of carbon dioxide (CO₂) threatens to change the earth's climate. A major factor in global warming is CO₂ emission from thermal power plants, which burn fossil fuels. One possible way of decreasing CO₂ emissions is to apply CO₂ removal, which involves recovering of CO₂ from energy conversion processes. This study is focused on recovery of CO₂ from gas turbine exhaust of Sarkhun gas refinery power station. The purpose of this study is to recover the CO₂ with minimum energy requirement. Many of CO₂ recovery processes from flue gases have been studied. Among all CO₂ recovery processes which were studied, absorption process was selected as the optimum one, due to low CO₂ concentration in flue gas. The design parameters considered in this regard, are: selection of suitable solvent, solvent concentration, solvent circulation rate, reboiler and condenser duty and number of stages in absorber and stripper columns. In the design of this unit, amine solvent such as, diethanolamine (DEA), diglycolamine (DGA), methyldiethanolamine (MDEA), and monoethanolamine (MEA) were considered and the effect of main parameters on the absorption and stripping columns is presented. Some results with simultaneous changing of the design variables have been obtained. The results show that DGA is the best solvent with minimum energy requirement for recovery of CO₂ from flue gases at atmospheric pressure.     

High performance composite hollow fiber membranes for CO2/H2 and CO2/N2 separation

The search for a clean energy source as well as the reduction of CO₂ emissions to the atmosphere are important strategies to resolve the current energy shortage and global warming issues. We have demonstrated, for the first time, a Pebax/poly(dimethylsiloxane)/polyacrylonitrile (Pebax/PDMS/PAN) composite hollow fiber membrane not only can be used for flue gas treatment but also for hydrogen purification. The composite membranes display attractive gas separation performance with a CO₂ permeance of 481.5 GPU, CO₂/H₂ and CO₂/N₂ selectivity of 8.1 and 42.0, respectively. Minimizing the solution intrusion using the PDMS gutter layer is the key to achieving the high gas permeance while the interaction between poly(ethylene oxide) (PEO) and CO₂ accounts for the high selectivity. Effects of coating solution concentration and coating time on gas separation performance have been investigated and the results have been optimized. To the best of our knowledge, this is the first polymeric composite hollow fiber membrane for hydrogen purification. The attractive gas separation performance of the newly developed membranes may indicate good potential for industrial applications.     

Production of H2 via thermal decomposition of H2S and separation of H2 and H2S by pressure swing adsorption

Preferable conditions for the thermal decomposition of hydrogen sulfide, one step in thermochemical water splitting cycles of metal-sulfur families, are described. To separate hydrogen from hydrogen sulfide after condensation of sulfur a pressure swing adsorption on zeolite or carbon molecular sieves is proposed which may also be suitable for separating hydrogen sulfide from other gas mixtures such as natural gas and noble gas.     

The solubility of Ni in molten Li2CO3–Na2CO3 (52/48) in H2/H2O/CO2 atmosphere

In this work the solubility of a Ni–Al anode for MCFC has been studied at atmospheric pressure and two different temperatures using various gas compositions containing H₂/H₂O/CO₂. It is well known that nickel is dissolved at cathode conditions in an MCFC. However, the results in this study show that nickel can be dissolved also at the anode, indicating that the solubility increases with increasing CO₂ partial pressure of the inlet gas and decreasing with increasing temperature. This agrees with the results found by other authors concerning the solubility of NiO at cathode conditions. The dissolution of Ni into the melt can proceed in two ways, either by the reduction of water or by the reduction of carbon dioxide.     

Load and weather profile,and time simulation impacts for the PEPITE PV/H2 project

This paper concerns the impacts of the meteorological data, the choice of the load profile, and the time simulation (1–11 years) on the energy flows and on the H₂/O₂/H₂O storage sizing in a photovoltaic/fuel cell/electrolyzer hybrid system (PEPITE project). The simulations were computed with the ORIENTE software. 4 load profiles have been investigated (3 diurnal and one nocturnal) with an identical daily consumption (26 kWh).     

Hydrogen permeation through a Pd-based membrane and RWGS conversion in H2/CO2, H2/N2/CO2 and H2/H2O/CO2 mixtures

This study investigated the effect of gases such as CO₂, N₂, H₂O on hydrogen permeation through a Pd-based membrane −0.012 m² – in a bench-scale reactor. Different mixtures were chosen of H₂/CO₂, H₂/N₂/CO₂ and H₂/H₂O/CO₂ at temperatures of 593–723 K and a hydrogen partial pressure of 150 kPa. Operating conditions were determined to minimize H₂ loss due to the reverse water gas shift (RWGS) reaction. It was found that the feed flow rate had an important effect on hydrogen recovery (HR). Furthermore, an identification of the inhibition factors to permeability was determined. Additionally, under the selected conditions, the maximum hydrogen permeation was determined in pure H₂ and the H₂/CO₂ mixtures. The best operating conditions to separate hydrogen from the mixtures were identified.     

Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants. Although the conventional steam reforming process is currently the most economical process for hydrogen production, the global energy and carbon efficiency of this process is still relatively low and an improvement of the process is key for further implementation of hydrogen as a fuel source. Different approaches for more efficient hydrogen production with integrated CO₂ capture have been discussed in literature: Chemical Looping Combustion (CLC) or Chemical Looping Reforming (CLR) and membrane reactors have been proposed as more efficient alternative reactor concepts relative to the conventional steam reforming process. However, these systems still present some drawbacks. In the present work a novel hybrid reactor concept that combines the CLR technology with a membrane reactor system is presented, discussed and compared with several other novel technologies. Thermodynamic studies for the new reactor concept, referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR), have been carried out to determine the hydrogen recovery, methane conversion as well as global efficiency under different operating conditions, which is shown to compare quite favorably to other novel technologies for H₂ production with CO₂ capture.     

CO2 and H2O gas conversion into CO and H2 using highly exothermic reactions induced by mixed industrial slags

This communication reports conversion phenomena in which CO₂ and H₂O gases are transformed into CO and H₂, respectively, when exposed to a mixture of molten CaO-rich metallurgical slag and V₂O₃-rich gasifier slag. On reaction, CO₂ and H₂O are thermodynamically driven to become CO and H₂, respectively, by giving up oxygen over the formation of calcium orthovanadate in the slag. The concept was experimentally investigated with a synthetic slag heated to 1500 °C (an assumed slag tap-out temperature in the metallurgical industry) in a CO₂ saturated atmosphere. On heating, a rapid drop in oxygen partial pressure occurred between 1405 °C and 1460 °C, where 97% of CO₂ transformed to CO. Potential industrial applications with the H₂O-to-H₂ conversion are then explored using detailed process computations. If the process is made economically viable, CO₂ and H₂O could be converted into products that are environmentally and industrially attractive and that have the potential for energy savings and greenhouse gas reduction in a process.     

Effect of H2S on carbon-catalyzed methane decomposition and CO2 reforming reactions

The effect of H₂S on catalytic processing of methane is of a great practical importance. In this work, the effect of small quantities (0.5–1.0 vol.%) of H₂S present in the feedstock on the methane decomposition and CO₂ reforming reactions over carbon and metal based catalysts was investigated. Activated carbon (FY5), an in-house prepared alumina-supported Ni catalyst (NiA) and the mixture of both (FY5 + NiA) were used as catalysts in this study. It was found that CH₄ and CO₂ conversions were noticeably increased when H₂S was added to the reacting mixture, which points to (i) the tolerance of carbon catalyst to H₂S and (ii) the catalytic effect of H₂S on carbon-catalyzed decomposition and dry reforming of methane. In contrast, NiA catalyst and the mixture FY5 + NiA were deactivated in the presence of H₂S in both reactions. The effect of the heating system (i.e., conventional electric resistance vs microwave heating) on the products yield of the dry reforming reaction in the presence of H₂S is also discussed in this paper.     

Ga homogenization by simultaneous H2Se/H2S reaction of Cu-Ga-In precursor

The compositional distribution of Ga and S in Cu(InGa)(SeS)₂ films fabricated by a simultaneous selenization and sulfization process was systematically investigated. At low H₂Se/H₂S reaction temperature (490 °C), most Ga remains at the back of the film adjacent to the Mo back contact. However, the Ga/III ratios at the top and bottom of the Cu(InGa)(SeS)₂ layer monotonically increase and decrease with reaction temperatures, respectively. At T>550 °C, homogeneous distribution of elemental Ga and In through film is achieved. Further increase of the reaction temperature (e.g., T>550 °C) causes phase segregation on the surface of the Cu(InGa)(SeS)₂ film confirmed by XRD, GIXRD and EDS analysis.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

Economic assessment of biogas-to-electricity generation system with H2S removal by activated carbon in small pig farm

This study was conducted to assess the economic feasibility of electricity generation from biogas in small pig farms with and without the H₂S removal prior to biogas utilisation. The 2% potassium iodide (KI) impregnated activated carbon selected as H₂S adsorbent was introduced to a biogas-to-electricity generation system in a small pig farm in Thailand as a case study. With the average inlet H₂S concentration of about 2400 ppm to the adsorption unit, the H₂S removal efficiency could reach 100% with the adsorption capacity of 0.062 kg of H₂S/kg of adsorbent. Under the reference scenario (i.e., 45% subsidy on digester installation and fixed electricity price at 0.06 Euro/kWh) and based on an assumption that the biogas was fully utilised for electricity generation in the system, the payback period for the system without H₂S removal was about 4 years. With H₂S removal, the payback period was within the economic life of digester but almost twice that of the case without H₂S removal. The impact of electricity price could be clearly seen for the case of treated biogas. At the electricity price fixed at 0.07 Euro/kWh, the payback period for the case of treated biogas was reduced to about 5.5 years, with a trend to decrease at higher electricity prices. For both treated and untreated biogas, the governmental subsidy was the important factor determining the economics of the biogas-to-electricity systems. Without subsidy, the payback period increased to almost 7 years and about 11 years for the case of untreated and treated biogas, respectively, at the reference electricity price. Although the H₂S removal added high operation cost to the system, it is still highly recommended not only for preventing engine corrosion but also for the environment benefit in which air pollution by H₂S/SO₂ emission and impact on human health could be potentially reduced.     

Assessment of existing H2/O2 chemical reaction mechanisms at reheat gas turbine conditions

This paper provides detailed comparisons of chemical reaction mechanisms of H₂ applicable at high preheat temperatures and pressures relevant to gas turbine and particularly Alstom’s reheat gas turbine conditions. It is shown that the available reaction mechanisms exhibit large differences in several important elementary reaction coefficients. The reaction mechanisms are assessed by comparing ignition delay and laminar flame speed results obtained from CHEMKIN with available data, however, the amount of data at these conditions is scarce and a recommended candidate among the mechanisms can presently not be selected. Generally, the results with the GRI-Mech and Leeds mechanisms deviate from the Davis, Li, Ó Conaire, Konnov and San Diego mechanisms, but there are also significant deviations between the latter five mechanisms that altogether are better adapted to hydrogen. The differences in ignition delay times between the dedicated hydrogen mechanisms (Ó Conaire, Li and Konnov) range from approximately a maximum factor of 2 for the H₂-air cases, to more than a factor 5 for the H₂/O₂/AR cases. The application of the computed ignition delay time to reheat burner development is briefly discussed.     

Bench-scale WGS membrane reactor for CO2 capture with co-production of H2

This study investigated the water-gas shift reaction in a bench-scale membrane reactor (M-WGS), where three supported Pd membranes of 44 cm in length and ca. 6 μm in thickness were used, reaching a total membrane surface area of 580.6 cm². The WGS reaction was studied with the syngas mixture: 4.0% CO, 19.2% CO₂, 15.4% H₂O, 1.2% CH₄ and 60.1% H₂, under high temperature/pressure conditions: T = 673 K, p_feed = 20–35 bar(a), p_perm = 15 bar(a), mimicking CO₂ capture with co-production of H₂ in a natural gas fired power plant. High reaction pressure and high permeation of Pd membranes allowed for near complete CO conversion and H₂ recovery. Both the membranes and the membrane reactor demonstrated a long-term stability under the investigated conditions, indicating the potential of M-WGS to substitute conventional systems.     

Experimental study on N2O emission in O2/CO2 combustion with high oxygen concentration in circulating fluidized bed

To characterize the N₂O formation and fuel nitrogen conversion in an oxy-fuel circulating fluidized bed (CFB) combustor with high oxygen concentration, tests were carried out by analysing the axial concentrations of N₂O in a 50 kW_th CFB combustor. The conversion ratios from fuel nitrogen to gaseous N-containing pollutants were calculated. The initial N₂O concentrations in the bottom of the combustor were similar between oxy-fuel firing and air-firing. The axial N₂O formation was more in oxy-fuel combustion than in air-firing, improving the N₂O emission during 50% O₂/50% CO₂ combustion. The atmospheric variation significantly affected the conversion ratio from fuel nitrogen to N₂O. In addition, the conversion from fuel nitrogen to N₂O was much higher than that to NO. As a result, the N₂O emission during oxy-fuel CFB combustion cannot be ignored. Gas staging little influenced the N₂O emission. With the increasing ratio of secondary gas, the initial N₂O formation in the dense zone increased, while the axial N₂O formation along the combustor declined. By analysing the conversion ratios of fuel nitrogen, it was also found that gas staging obviously affected the conversion ratio from fuel nitrogen to NO by enhancing the NO to N₂ conversion. However, gas staging did not impact the conversion ratio from fuel nitrogen to N₂O.     

CO2 methanation combined with NH3 decomposition by in situ H2 separation using a Pd membrane reactor

Combination of the reactions by means of membrane separation techniques are of interest. The CO₂ methanation was combined with NH₃ decomposition by in situ H₂ separation through a Pd membrane. The CO₂ methanation reaction in the permeate side was found to significantly enhance the H₂ removal rate of Pd membrane compared to the use of sweep gas. The reaction rate of CO₂ methanation was not influenced by H₂ supply through the Pd membrane in contrast to NH₃ decomposition in the retentate side. However, the CH₄ selectivity could be improved by using a membrane separation technique. This would be caused by the active dissociated H species which might immediately react with adsorbed CO species on the catalysts to CH₄ before those CO species desorbed. From the reactor configuration tests, the countercurrent mode showed higher H₂ removal rate in the combined reaction at 673 K compared to the cocurrent mode but the reaction rate in CO₂ methanation should be improved to maximize the perfomance of membrane reactor.     

A theoretical analysis of methanol synthesis from CO2 and H2 in a ceramic membrane reactor

In this theoretical work the CO₂ conversion into methanol in both a traditional reactor (TR) and a membrane reactor (MR) is considered. The purpose of this study was to investigate the possibility of increasing CO₂ conversion into methanol with respect to a TR. A zeolite MR, able to combine catalytic reactions with separation properties of zeolite membranes, which allows only vapours to permeate, is considered. A mathematical model is used to simulate a traditional chemical reactor: a comparison among the model results and literature experimental data confirmed the validity of the model. Afterwards, the model is used to predict the behaviour of a zeolite MR in terms of both CO₂ conversion and methanol selectivity. The results show that it is possible to obtain both higher CO₂ conversion and methanol selectivity with respect to a TR operating at the same experimental conditions.     

Continuous purification of H2SO4 and HI phases by packed column in IS process

Iodine–sulfur (IS) thermo-chemical water-splitting process is a promising technology to produce hydrogen using solar or nuclear energy. To avoid the undesirable side reactions between HI and H₂SO₄ phases formed in Bunsen reaction of IS cycle, it is necessary to purify the two phases. The purification process could be achieved by reverse reaction of Bunsen reaction. In this paper, the purification process in continuous mode by reacting sulfuric acid and HI in a packed column was experimentally studied; the influences of operational parameters, including the reaction temperature, the flow rate of nitrogen gas, and the flow rate of the raw material solutions, on the purification efficiency, were investigated in detail. Based on the results, the suitable conditions for continuous purification process of two phases were proposed.     

A parametric investigation of hydrogen energy potential based on H2S in Black Sea deep waters

In this study, a parametric investigation is carried out to estimate the hydrogen energy potential depending on the quantities of H₂S in Black Sea deep waters. The required data for H₂S in Black Sea deep waters are taken from the literature. For this investigation, the H₂S concentration and water layer depth are taken into account, and 100% of conversion efficiency is assumed. Consequently, it is estimated that total hydrogen energy potential is approximately 270 million tons produced from 4.587 billion tons of H₂S in Black Sea deep waters. Using this amount of hydrogen, it will be possible to produce 38.3 million TJ of thermal energy or 8.97 million GWh of electricity energy. Moreover, it is determined that total hydrogen potential in Black Sea deep waters is almost equal to 808 million tons of gasoline or 766 million tons of NG (natural gas) or 841 million tons of fuel oil or 851 million tons of natural petroleum. These values show that the hydrogen potential from hydrogen sulphur in Black Sea deep water will play an important role to supply energy demands of the regional countries. Thus, it can be said that hydrogen energy reserve in Black Sea is an important candidate for the future hydrogen energy systems.