Thermodynamic evaluation of methanol steam reforming for hydrogen production

Thermodynamic equilibrium of methanol steam reforming (MeOH SR) was studied by Gibbs free minimization for hydrogen production as a function of steam-to-carbon ratio (S/C = 0–10), reforming temperature (25–1000 °C), pressure (0.5–3 atm), and product species. The chemical species considered were methanol, water, hydrogen, carbon dioxide, carbon monoxide, carbon (graphite), methane, ethane, propane, i-butane, n-butane, ethanol, propanol, i-butanol, n-butanol, and dimethyl ether (DME). Coke-formed and coke-free regions were also determined as a function of S/C ratio.Based upon a compound basis set MeOH, CO₂, CO, H₂ and H₂O, complete conversion of MeOH was attained at S/C = 1 when the temperature was higher than 200 °C at atmospheric pressure. The concentration and yield of hydrogen could be achieved at almost 75% on a dry basis and 100%, respectively. From the reforming efficiency, the operating condition was optimized for the temperature range of 100–225 °C, S/C range of 1.5–3, and pressure at 1 atm. The calculation indicated that the reforming condition required from sufficient CO concentration (<10 ppm) for polymer electrolyte fuel cell application is too severe for the existing catalysts (T_r = 50 °C and S/C = 4–5). Only methane and coke thermodynamically coexist with H₂O, H₂, CO, and CO₂, while C₂H₆, C₃H₈, i-C₄H₁₀, n-C₄H₁₀, CH₃OH, C₂H₅OH, C₃H₇OH, i-C₄H₉OH, n-C₄H₉OH, and C₂H₆O were suppressed at essentially zero. The temperatures for coke-free region decreased with increase in S/C ratios. The impact of pressure was negligible upon the complete conversion of MeOH.     

Syngas production by gasification of aquatic biomass with CO2/O2 and simultaneous removal of H2S and COS using char obtained in the gasification

Applicability of gulfweed as feedstock for a biomass-to-liquid (BTL) process was studied for both production of gas with high syngas (CO + H₂) content via gasification of gulfweed and removal of gaseous impurities using char obtained in the gasification. Gulfweed as aqueous biomass was gasified with He/CO₂/O₂ using a downdraft fixed-bed gasifier at ambient pressure and 900 °C at equivalence ratios (ER) of 0.1–0.3. The syngas content increased while the conversion to gas on a carbon basis decreased with decreasing ER. At an ER of 0.1 and He/CO₂/O₂ = 0/85/15%, the syngas content was maximized at 67.6% and conversion to gas on a carbon basis was 94.2%. The behavior of the desulfurization using char obtained during the gasification process at ER = 0.1 and He/CO₂/O₂ = 0/85/15% was investigated using a downdraft fixed-bed reactor at 250–550 °C under 3 atmospheres (H₂S/N₂, COS/N₂, and a mixture of gases composed of CO, CO₂, H₂, N₂, CH₄, H₂S, COS, and steam). The char had a higher COS removal capacity at 350 °C than commercial activated carbon because (Ca,Mg)S crystals were formed during desulfurization. The char simultaneously removed H₂S and COS from the mixture of gases at 450 °C more efficiently than did activated carbon. These results support this novel BTL process consisting of gasification of gulfweed with CO₂/O₂ and dry gas cleaning using self-supplied bed material.     

Hydrogen production and CO2 fixation by flue-gas treatment using methane tri-reforming or coke/coal gasification combined with lime carbonation

The production of hydrogen and the fixation of CO₂ can be achieved by treatment of flue gases derived from fossil fuel fired power plants via catalytic methane tri-reforming or by coal gasification in the presence of CaO. A two-step process is designed to be carried out in two reactors: a) a catalytic gasifier or steam-reformer, operating exothermally at 900–1000 K, with inputs of the flue gas, a carbonaceous source, steam and air, as well as CaO from the calciner, and outputs of H₂, and of “spent” CaCO₃ to the calciner; b) a calciner, operating endothermally at 1100–1300 K, with inputs of spent CaCO₃ from the gasifier, make-up fresh CaCO₃, and outputs of CO₂, as well as of CaO, partly recycled to the gasifier and partly processed in a cement plant. Thermochemical equilibrium calculations along with mass/energy balances indicate that for flue-gas treatment by tri-reforming, CO₂ emission avoidance of up to ∼59% and fossil fuel savings of up to ∼75% may be attained when concentrated solar energy is supplied as high-temperature process heat for the calcination step, all relative to conventional H₂ production by coal gasification. If instead fossil fuel would be used to drive the calcination step, the CO₂ emission avoidance and the fuel savings would be only 20% and 67%, respectively. Estimated annual H₂ production from a coal-fired 500 MWe burner by the proposed flue-gas treatment using either CH₄-tri-reforming or coal gasification would amount to 0.7 × 10⁶ or 0.6 × 10⁶ metric tons H₂, respectively. Estimated fossil fuel consumption for H₂ production by tri-reforming or coke gasification would be 149 or 143 GJ fuel/ton H₂.     

Effect of CaO hydration and carbonation on the hydrogen production from sorption enhanced water gas shift reaction

Sorption enhanced water gas shift reaction (SEWGS) based on calcium looping is an emerging technology for hydrogen production and CO₂ capture. SEWGS involves mainly two reactions, the catalytic WGS reaction and the bulk carbonation of CaO with CO₂, and the solid product is CaCO₃, and the Ca(OH)₂ may be formed from the reaction of CaO with H₂O with the presence of steam in gas phase. The effect of Ca(OH)₂ and CaCO₃ on the catalytic WGS reaction and carbonation reaction was studied in a fluidized bed reactor. It was found that the hydrated sorbent and CaCO₃ did not show any catalytic reactivity toward WGS reaction at 400 °C. When the temperature was increased to 500 °C and 600 °C, the catalytic reactivity of hydrated sorbent was recovered partially, but this will depend on the steam fraction in gas phase, the recovery of fresh CaO surface from dehydration of Ca(OH)₂ may be the reason of catalytic reactivity recovery. CaCO₃ can catalyze the WGS reaction at the high-temperature (>600 °C), this may due to the CaCO₃ decomposition and recarbonation processes in which the CaO is transiently formed. The possible mechanism was discussed.     

Enhanced hydrogen-rich gas production from steam gasification of coal in a pressurized fluidized bed with CaO as a CO2 sorbent

Steam gasification of a typical Chinese bituminous coal for hydrogen production in a lab-scale pressurized bubbling fluidized bed with CaO as CO₂ sorbent was performed over a pressure range of ambient pressure to 4 bar. The compositions of the product gases were analyzed and correlated to the gasification operating variables that affecting H₂ production, such as pressure (P), mole ratio of steam to carbon ([H₂O]/[C]), mole ratio of CaO to carbon ([CaO]/[C]) and temperature (T). The experimental results indicated that the H₂ concentration was enhanced by raising the temperature, pressure and [H₂O]/[C] under the circumstances we observed. With the presence of CaO sorbent, CO₂ in the production gas was absorbed and converted to solid CaCO₃, thus shifting the steam reforming of hydrocarbons and water gas shift reaction beyond the equilibrium restrictions and enhancing the H₂ concentration. H₂ concentration was up to 78 vol% (dry basis) under a condition of 750 °C, 4 bar, [Ca]/[C] = 1 and [H₂O]/[C] = 2, while CO₂ (2.7 vol%) was almost in-situ captured by the CaO sorbent. This study demonstrated that CaO could be used as a substantially excellent CO₂ sorbent for the pressurized steam gasification of bituminous coal. For the gasification process with the presence of CaO, H₂-rich syngas was yielded at far lower temperatures and pressures in comparison to the commercialized coal gasification technologies. SEM/EDX and gas sorption analyses of solid residues sampled after the gasification showed that the pore structure of the sorbent was recovered after the steam gasification process, which was attributed to the formation of Ca(OH)₂. Additionally, a coal-CaO–H₂O system was simulated with using Aspen Plus software. Calculation results showed that higher temperatures and pressures favor the H₂ production within a certain range.     

Coal-gasification kinetics derived from pyrolysis in a fluidized-bed reactor

Coal pyrolysis and gasification reactions were carried out in a fluidized-bed reactor (0.1 m i.d. by 1.6 m height) over a temperature range from 1023 to 1173 K at atmospheric pressure. The overall gasification kinetics for the steam–char and oxygen–char reactions were determined in a thermobalance reactor. The compositions of the product gases from the coal-gasification reactions are 30–40% H₂, 23–28% CO, 27–35% CO₂ and 6–9% CH₄ with heating values of 2000–3750 kJ m⁻³. The heating value increases with increasing temperature and steam/coal ratio but decreases with increasing air/coal ratio. Our kinetic data derived from the two-phase theory on coal gasification in a thermobalance reactor and coal pyrolysis in a fluidized bed may be used to predict the product-gas compositions.     

Study of Ce-Pt/γ-Al2O3 for the selective oxidation of CO in H2 for application to PEFCs: Effect of gases

In order to supply pure hydrogen to proton exchange membrane (PEM) fuel cells and avoid CO poisoning, selective CO oxidation in H₂ was studied over Ce-Pt/γ-Al₂O₃. Adding the Ce promoted the CO conversion and selectivity of Pt/γ-Al₂O₃ with changing loading weights of Pt and Ce, oxygen concentration, residence time, and the composition of gases (H₂O, CO₂, and N₂). At 250 °C, adding H₂O to the feed gas enhanced the CO conversion due to the water–gas shift reaction. While, adding CO₂ to the feed gas suppressed the CO conversion due to the reversible water–gas shift reaction. In situ BET and XRD tests showed that well-dispersed metallic Pt particles (−2 nm) existed on the Ce oxide over the alumina support, which helps to supply oxygen to the Pt for a high activity of CO oxidation and selectivity.     

100 t/a-Scale demonstration of direct dimethyl ether synthesis from corncob-derived syngas

Direct conversion of biomass-derived syngas (bio-syngas) to dimethyl ether (DME) at pilot-scale (100 t/a) was carried out via pyrolysis/gasification of corncob. The yield rate of raw bio-syngas was 40–45 Nm³/h with less than 20 mg/Nm³ of tar content when the feedrate of dried corncob was 45–50 kg/h. After absorption of O₂, S, Cl by a series of absorbers and partial removal of CO₂ by the pressure-swing adsorption (PSA) unit sequentially, the obtained bio-syngas (H₂/CO≈1) was directly synthesized to DME over Cu/Zn/Al/HZSM-5 catalyst in the fixed-bed tubular reactor. CO conversion and DME space-time yield (STY) were 67.7% and 281.2 kg/m_cat³/h respectively at 260 °C, 4.3 MPa and 3000 h^?1(GHSV, syngas hourly space velocity). Synthesis performance would be increased if the tail gas (H₂/CO > 2) was recycled to the reactor when GHSV was 650–3000 h^?1.     

Effects of dilution with carbon dioxide on the laminar burning velocity and flame stability of H2–CO mixtures at atmospheric condition

The objective of this investigation was to study the effect of dilution with CO₂ on the laminar burning velocity and flame stability of syngas fuel (50% H₂–50% CO by volume). Constant pressure spherically expanding flames generated in a 40 l chamber were used for determining unstretched burning velocity. Experimental and numerical studies were carried out at 0.1 MPa, 302 ± 3 K and ? = 0.6–3.0 using fuel-diluent and mixture-diluent approaches. For H₂–CO–CO₂–O₂–N₂ mixtures, the peak burning velocity shifts from ? = 2.0 for 0% CO₂ in fuel to ? = 1.6 for 30% CO₂ in fuel. For H₂–CO–O₂–CO₂ mixtures, the peak burning velocity occurred at ? = 1.0 unaffected by proportion of CO₂ in the mixture. If the mole fraction of combustibles in H₂–CO–O₂–CO₂ mixtures is less than 32%, then such mixtures are supporting unstable flames with respect to preferential diffusion. The analysis of measured unstretched laminar burning velocities of H₂–CO–O₂–CO₂ and H₂–CO–O₂–N₂ mixtures suggested that CO₂ has a stronger inhibiting effect on the laminar burning velocity than nitrogen. The enhanced dilution effect of CO₂ could be due to the active participation of CO₂ in the chemical reactions through the following intermediate reaction CO + OH ? CO₂ + H.     

Hydrogen production for fuel cells through methane reforming at low temperatures

Hydrogen production for fuel cells through methane (CH₄) reforming at low temperatures has been investigated both thermodynamically and experimentally. From the thermodynamic equilibrium analysis, it is concluded that steam reforming of CH₄ (SRM) at low pressure and a high steam-to-CH₄ ratio can be achieved without significant loss of hydrogen yield at a low temperature such as 550 °C. A scheme for the production of hydrogen for fuel cells at low temperatures by burning the unconverted CH₄ to supply the heat for SRM is proposed and the calculated value of the heat-balanced temperature is 548 °C. SRM with and/or without the presence of oxygen at low temperatures is experimentally investigated over a Ni/Ce–ZrO₂/θ-Al₂O₃ catalyst. The catalyst shows high activity and stability towards SRM at temperatures from 400 to 650 °C. The effects of O₂:CH₄ and H₂O:CH₄ ratios on the conversion of CH₄, the hydrogen yield, the selectivity for carbon monoxide, and the H₂:CO ratio are investigated at 650 °C with a constant CH₄ space velocity. Results indicate that CH₄ conversion increases significantly with increasing O₂:CH₄ or H₂O:CH₄ ratio, and the hydrogen content in dry tail gas increases with the H₂O:CH₄ ratio.     

Negative pressure dependence of mass burning rates of H2/CO/O2/diluent flames at low flame temperatures

Experimental measurements of burning rates, analysis of the key reactions and kinetic pathways, and modeling studies were performed for H₂/CO/O₂/diluent flames spanning a wide range of conditions: equivalence ratios from 0.85 to 2.5, flame temperatures from 1500 to 1800 K, pressures from 1 to 25 atm, CO fuel fractions from 0 to 0.9, and dilution concentrations of He up to 0.8, Ar up to 0.6, and CO₂ up to 0.4. The experimental data show negative pressure dependence of burning rate at high pressure, low flame temperature conditions for all equivalence ratios and CO fractions as high as 0.5. Dilution with CO₂ was observed to strengthen the pressure and temperature dependence compared to Ar-diluted flames of the same flame temperature. Simulations were performed to extend the experimentally studied conditions to conditions typical of gas turbine combustion in Integrated Gasification Combined Cycle processes, including preheated mixtures and other diluents such as N₂ and H₂O.Substantial differences are observed between literature model predictions and the experimental data as well as among model predictions themselves – up to a factor of three at high pressures. The present findings suggest the need for several rate constant modifications of reactions in the current hydrogen models and raise questions about the sufficiency of the set of hydrogen reactions in most recent hydrogen models to predict high pressure flame conditions relevant to controlling NO_x emissions in gas turbine combustion. For example, the reaction O + OH + M = HO₂ + M is not included in most hydrogen models but is demonstrated here to significantly impact predictions of lean high pressure flames using rates within its uncertainty limits. Further studies are required to reduce uncertainties in third body collision efficiencies for and fall-off behavior of H + O₂(+M) = HO₂(+M) in both pure and mixed bath gases, in rate constants for HO₂ reactions with other radical species at higher temperatures, and in rate constants for reactions such as O + OH + M that become important under the present conditions in order to properly characterize the kinetics and predict global behavior of high-pressure H₂ or H₂/CO flames.     

Alkalinity and high total solids affecting H2 production from organic solid waste by anaerobic consortia

The optimization of total solids in the feed (%TS) and alkalinity ratio (γ) for H₂ production from organic solid wastes under thermophilic regime was carried out using response surface methodology based on a central composite design. The total solids levels were 20.9, 23.0, 28.0, 33.0 and 35.1% whereas the levels of alkalinity ratio (defined as g phosphate alkalinity/g dry substrate) were 0.15, 0.20, 0.30, 0.41 and 0.45. High levels of TS and γ affected in a negative way the H₂ productivity and yield; both response variables significantly increased upon decreasing the TS content and alkalinity ratio. The highest H₂ productivity and yield were 463.7 N mL/kg-d and 54.8 N mL/g VS_rem, respectively, predicted at 20.9% TS and alkalinity ratio 0.25 (0.11 g CaCO₃/g dry substrate). The alkalinity requirements for hydrogenogenic processes were lower than those reported for methanogenic processes (0.11 vs. 0.30 g CaCO₃/g COD). Adequate alkalinity ratio was necessary to maintain optimal biological activity for hydrogen production; however, excessive alkalinity negatively affected process performance probably due to an increase of osmotic pressure. Interestingly, reactor pH depended only on the alkalinity ratio, thus the buffer capacity was able to maintain a constant pH independently of TS levels. At γ = 0.15–0.30 the pHs were in the range 5.56–5.95, which corresponded to the highest hydrogen productivities and yields. Finally, the highest metabolite accumulation corresponded with the highest removal efficiencies but not with high H₂ productivities and yields. Therefore, it seems that organic matter removal was channeled toward solvent generation instead of hydrogen production at high TS and γ levels. This is the first study that shows the requirements of alkalinity in solid substrate fermentation conditions for H₂ production processes and their interaction with the content of total solids in the feed.     

The capacitive characteristics of activated carbons—comparisons of the activation methods on the pore structure and effects of the pore structure and electrolyte on the capacitive performance

Fir wood-derived carbons activated with steam, KOH, and KOH + CO₂ were found to exhibit the high-power, low ESR, and highly reversible characteristics between −0.1 and 0.9 V in aqueous electrolytes, which were demonstrated to be promising electrode materials for supercapacitors. The pore structure of these activated carbons was systematically characterized by the t-plot method based on N₂ adsorption isotherms. Activated carbons prepared through the above three activation methods under different conditions (i.e., the gasification time of CO₂, KOH/char ratio, and activation time of steam) generally showed excellent capacitive performance in aqueous media, mainly attributed to the development of both micropores and mesopores (with the meso-pore volume ratio, V_meso/V_pore, ranging from 0.18 to 0.52). Scanning electron microscopic (SEM) photographs showed that the surface morphologies of honeycombed holes were found to depend on the activation methods. The average specific capacitance of the activated carbon with a combination of KOH etching and CO₂ gasification (with gasification time of 15 min) reached 197 F g⁻¹ between −0.1 and 0.9 V in H₂SO₄. The capacitive characteristics of steam- and KOH-activated carbons in NaNO₃ and H₂SO₄ could be roughly estimated from the pore structure and BET surface area although the correlation may be only applicable for the fir wood-derived activated carbons.     

Upgrading of syngas derived from biomass gasification: A thermodynamic analysis

Hydrogen yields in the syngas produced from non-catalytic biomass gasification are generally low. The hydrogen fraction, however, can be increased by converting CO, CH₄, higher hydrocarbons, and tar in a secondary reactor downstream. This paper discusses thermodynamic limits of the synthesis gas upgrading process. The method used in this process is minimization of Gibbs free energy function. The analysis is performed for temperature ranges from 400 to 1300 K, pressure of 1–10 atm (0.1–1 MPa), and different carbon to steam ratios. The study concludes that to get optimum H₂ yields, with negligible CH₄ and coke formation, upgrading syngas is best practiced at a temperature range of 900–1100 K. At these temperatures, H₂ could be possibly increased by 43–124% of its generally observed values at the gasifier exit. The analysis revealed that increasing steam resulted in a positive effect. The study also concluded that increasing pressure from 1 to 3 atm can be applied at a temperature >1000 K to further increase H₂ yields.     

Investigation of a novel & integrated simulation model for hydrogen production from lignocellulosic biomass

Process simulation and modeling works are very important to determine novel design and operation conditions. In this study; hydrogen production from synthesis gas obtained by gasification of lignocellulosic biomass is investigated. The main motivation of this work is to understand how biomass is converted to hydrogen rich synthesis gas and its environmentally friendly impact. Hydrogen market development in several energy production units such as fuel cells is another motivation to realize these kinds of activities. The initial results can help to contribute to the literature and widen our experience on utilization of the CO₂ neutral biomass sources and gasification technology which can develop the design of hydrogen production processes. The raw syngas is obtained via staged gasification of biomass, using bubbling fluidized bed technology with secondary agents; then it is cleaned, its hydrocarbon content is reformed, CO content is shifted (WGS) and finally H₂ content is separated by the PSA (Pressure Swing Adsorption) unit. According to the preliminary results of the ASPEN HYSYS conceptual process simulation model; the composition of hydrogen rich gas (0.62% H₂O, 38.83% H₂, 1.65% CO, 26.13% CO₂, 0.08% CH₄, and 32.69% N₂) has been determined. The first simulation results show that the hydrogen purity of the product gas after PSA unit is 99.999% approximately. The mass lower heating value (LHV_mass) of the product gas before PSA unit is expected to be about 4500 kJ/kg and the overall fuel processor efficiency has been calculated as ～93%.     

Iron ore as oxygen carrier improved with potassium for chemical looping combustion of anthracite coal

Chemical looping combustion (CLC) is an innovative combustion technology with inherent separation of CO₂ without energy penalty. When solid fuel is applied in CLC, the gasification of solid fuel is the rate-limiting process for in situ gasification of coal and reduction of oxygen carrier. The K₂CO₃-decorated iron ore after calcinations was used as oxygen carrier in CLC of anthracite coal, and potassium ferrites were formed during the calcinations process. The experiments were performed in a laboratory fluidized bed reactor with steam as a gasification medium. Effects of reaction temperature, K₂CO₃ loading in iron ore and cycle on the gas concentration, carbon conversion, gasification rate and yields of carbonaceous gases were investigated. The carbon gasification was accelerated during the fast reaction stage between 860 °C and 920 °C, and the water–gas shift reaction was significantly enhanced in a wider temperature range of 800 °C to 920 °C. With the K₂CO₃ loading in iron ore increasing from 0% to 20% at 920 °C, the carbon conversion was accelerated in the fast reaction stage, and the fast reaction stage became shorter. The yield of CO₂ reached a maximum of 94.4% and the yield of CO reached a minimum of 3.4% when use the iron ore loaded with 6% K₂CO₃. SEM analysis showed that the K₂CO₃-decorating in iron ore would cause a sintering on the particle surface of oxygen carrier, and the K₂CO₃ loading in iron ore should not be too high. Cycle experiments indicate that the K₂CO₃-decorated iron ore has a relative stable catalytic effect in the CLC process.     

Hydrogen production by gasification of Kenaf under subcritical liquid‒vapor phase conditions

In this study, Kenaf biomass was gasified under subcritical liquid-vapor conditions and effect of initial water amount on gas composition and hydrogen production was evaluated at different temperatures. Gasification was carried out in a batch type reactor, with various initial water volumes (0, 12, 25, 50, 75 mL), at different temperatures (250, 275, 300, 325 °C) and with different catalysts (Ru/C, Pt/C, Na₂CO₃, Fe₂O₃, CaO, CaCO₃ and RuCl₃). The results revealed that the gasification efficiency and hydrogen selectivity are dramatically varied with initial water percentage that was fed to the reactor. The gaseous products obtained from hydrothermal gasification of kenaf were mainly H₂, CO₂, and in lower but varying amounts, CH₄ and C₂H₄. Water soluble RuCl₃ was found to be more effective than water insoluble Ru/C catalyst on biomass gasification. RuCl₃ catalyst has a high catalytic activity for kenaf gasification with greater H₂ selectivity. Maximum total gas (462.5 mL) and H₂ mole fraction in the gaseous product (44.5%) were obtained at 250 °C with RuCl₃ catalyst. The maximum carbon conversion (%) was also obtained with RuCl₃ as 71.3%. Water behaves as both the reaction medium and the second main reactant beside biomass, during the subcritical liquid-vapor phase gasification process.     

Thermodynamic analysis of a biomass anaerobic gasification process for hydrogen production with sufficient CaO

Based on CO₂ acceptor gasification technology, a biomass anaerobic gasification technology for H₂ production was proposed. Utilizing thermodynamic equilibrium calculation software FactSage 5.2, the rules of biomass/CaO/H₂O and C/CaCO₃/air reaction system involved in this H₂ production technology were studied. The results show that the increase of CaO can obviously increase H₂ mole fraction in C/H₂O reaction products. When the mole ratio of CaO to carbon ([Ca]/[C]) is 1, H₂ concentration may achieve the maximum value. The H₂ amount obviously increases, and H₂ mole fraction decreases slightly with increasing reaction pressure in a specific range. Higher reaction temperature obviously decreases the amount and mole fraction of H₂. There are different maximum temperatures which are suitable for H₂ production under various pressures. Increasing of the mole ratio of H₂O to carbon of biomass ([H₂O]/[C]) is helpful for H₂ production. But the H₂ mole fraction is reduced with the increasing of [H₂O]/[C] when it exceeds 1.5. The calculations of linear sensitivity coefficient show that [H₂O]/[C] has the greatest influence on H₂ production efficiency, the influence of reaction pressure and temperature are also obvious. Compared with the coal gasification for H₂ production, the excess of H₂O in biomass anaerobic gasification system is relatively obvious. Lower reaction pressure is helpful for CaO regeneration in the C/CaCO₃/air reaction system, and there are different minimum temperatures which CaO regeneration needs under various reaction pressures.     

ZECOMIX: Performance of alternative lay-outs

ZECOMIX is a plant for hydrogen production and power generation using coal as a primary energy source and with nearly zero emissions. The global lay-out can be divided in 5 sectors: coal gasification, O₂ production, CO₂ capture, CO₂ sequestration, power generation. Coal is hydro gasified using a stream of hydrogen internally recycled. The syngas, mainly methane, is then reformed with steam and CaO in such a way to obtain a gaseous stream of hydrogen and steam separated from CaCO₃ which is solid. CaO is then regenerated inside a calciner which produce also a gaseous stream of CO₂ which has to be stored. The stream of hydrogen is burned with stoichiometric O₂ and the resulting steam is expanded in a steam power plant. After having focused our efforts on the coal gasification and CO₂ capture, we selected a layout for these sections and analysed the possibility to cogenerate hydrogen and power. The results confirmed that cogeneration is the most efficient solution and ZECOMIX seems to be an interesting option.     

H2S effect on dry reforming of biogas for syngas production

The effect of hydrogen sulfide (H₂S) on dry reforming of biogas for syngas production was studied both experimentally and theoretically. In the experimental work, the H₂S effect on Ni‐based catalyst activity was examined for reaction temperatures ranging from 600°C to 800°C. It was found that the presence of H₂S deactivated the Ni‐based catalysts significantly because of sulfur poisoning. Although bimetallic Pt‐Ni catalyst has better performance compared with monometallic Ni catalyst, deactivation was still found. The time‐on‐stream measured data also indicated that sulfur‐poisoned catalyst can be regenerated at high reaction temperatures. In the theoretical work, a thermodynamic equilibrium model was used to analyze the H₂S removal effect in dry reforming of H₂S‐contained biogas. Calcium oxide (CaO) and calcium carbonate (CaCO₃) were used as the H₂S sorbent. The results indicated that H₂S removal depends on the initial H₂S concentration and reaction temperature for both sorbents. Although CO₂ was also removed by CaO, the results from equilibrium analysis indicated that the dry reforming reaction in the presence of CaO was feasible similar to the sorption enhanced water‐gas shift and steam‐methane reforming reactions. The simulation results also indicated that CaO was a more preferable H₂S sorbent than CaCO₃ because syngas with an H₂/CO ratio closer to 2 can be produced and requires lower heat duty.