Solar syngas production from CO2 and H2O in a two-step thermochemical cycle via Zn/ZnO redox reactions: Thermodynamic cycle analysis

Solar syngas production from CO₂ and H₂O is considered in a two-step thermochemical cycle via Zn/ZnO redox reactions, encompassing: 1) the ZnO thermolysis to Zn and O₂ using concentrated solar radiation as the source of process heat, and 2) Zn reacting with mixtures of H₂O and CO₂ yielding high-quality syngas (mainly H₂ and CO) and ZnO; the ZnO is recycled to the first, solar step, resulting in net reaction βCO₂ + (1 − β)H₂O → βCO + (1 − β)H₂. Syngas is further processed to liquid hydrocarbon fuels via Fischer-Tropsch or other catalytic processes. Second-law thermodynamic analysis is applied to determine the cycle efficiencies attainable with and without heat recuperation for varying molar fractions of CO₂:H₂O and solar reactor temperatures in the range 1900-2300 K. Considered is the energy penalty of using Ar dilution in the solar step below 2235 K for shifting the equilibrium to favor Zn production.     

The thermodynamic analysis of two-step conversions of CO2/H2O for syngas production by ceria

Due to the challenges of demands on alternative fuels and CO₂ emission, the conversion of CO₂ has become a hot spot. Among various methods, two-step conversion of CO₂ with catalyst ceria (cerium oxide, CeO₂) appears to be a promising way. Solar energy is commonly employed to drive the conversion systems. This article proposes a solar-driven system with fluidized bed reactors (FBR) for CO₂/H₂O conversions. N₂ is used as the gas of the heat carrier. The products of CO/H₂ could be further used for syngas. To evaluate the capability of the system for exporting work, the system was analysed on the basis of the Second Law of Thermodynamics and the reaction mechanism of ceria. Heat transfer barriers in practical situations were considered. The lowest solar to chemical efficiency is 4.86% for CO₂ conversion, and can be enhanced to 43.2% by recuperating waste heat, raising the N₂ temperature, and increasing the concentration ratio. The analysis shows that the method is a promising approach for CO₂/H₂O conversion to produce syngas as an alternative fuel.     

Controllable proton and CO2 photoreduction over Cu2O with various morphologies

Simultaneous photocatalytic reduction of water to H₂ and CO₂ to CO was observed over Cu₂O photocatalyst under both full arc and visible light irradiation (>420 nm). It was found that the photocatalytic reduction preference shifts from H₂ (water splitting) to CO (CO₂ reduction) by controlling the exposed facets of Cu₂O. More interestingly, the low index facets of Cu₂O exhibit higher activity for CO₂ photoreduction than high index facets, which is different from the widely-reported in which the facets with high Miller indices would show higher photoactivity. Improved CO conversion yield could be further achieved by coupling the Cu₂O with RuO_x to form a heterojunction which slows down fast charge recombination and relatively stabilises the Cu₂O photocatalyst. The RuO_x amount was also optimised to maximise the junction's photoactivity.     

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.     

Comparative study on the effect of CO2 and H2O dilution on laminar burning characteristics of CO/H2/air mixtures

A study on the effect of CO₂ and H₂O dilution on the laminar burning characteristics of CO/H₂/air mixtures was conducted at elevated pressures using spherically expanding flames and CHEMKIN package. Experimental conditions for the CO₂ and H₂O diluted CO/H₂/air/mixtures of hydrogen fraction in syngas from 0.2 to 0.8 are the pressures from 0.1 to 0.3 MPa, initial temperature of 373 K, with CO₂ or H₂O dilution ratios from 0 to 0.15. Laminar burning velocities of the CO₂ and H₂O diluted CO/H₂/air/mixtures were measured and calculated using the mechanism of Davis et al. and the mechanism of Li et al. Results show that the discrepancy exists between the measured values and the simulated ones using both Davis and Li mechanisms. The discrepancy shows different trends under CO₂ and H₂O dilution. Chemical kinetics analysis indicates that the elementary reaction corresponding to peak ROP of OH consumption for mixtures with CO/H₂ ratio of 20/80 changes from reaction R3 (OH + H₂ = H + H₂O) to R16 (HO₂+H = OH + OH) when CO₂ and H₂O are added. Sensitivity analysis was conducted to find out the dominant reaction when CO₂ and H₂O are added. Laminar burning velocities and kinetics analysis indicate that CO₂ has a stronger chemical effect than H₂O. The intrinsic flame instability is promoted at atmospheric pressure and is suppressed at elevated pressure for the CO₂ and H₂O diluted mixtures. This phenomenon was interpreted with the parameters of the effective Lewis number, thermal expansion ratio, flame thickness and linear theory.     

Flowerlike microspheres catalyst NiO/La2O3 for ethanol-H2 production

Catalysts of nano-sized nickel oxide particles based on flowerlike lanthanum oxide microspheres with high disperse were prepared to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, SEM, 77K N₂ adsorption were used to analyze and observe the catalysts’ structure, morphology and porosity. Catalytic parameters with respect to yield of H₂, activity, selectivity towards gaseous products and stability with time-on-stream and time-on-off-stream were all determined. This special morphology NiO/La₂O₃ catalyst represented more than 1000 h time-on-stream stability test and 500 h time-on-off-stream stability test for hydrogen fuel production from ethanol steam reforming at 300 °C without any deactivation. During the 1000 h time-on-stream stability test, ethanol–water mixtures could be converted into H₂, CO, and CH₄ with average selectivity values of 57.0, 20.1, 19.6 and little CO₂ of 3.2 mol%, respectively, and average ethanol conversion values of 96.7 mol%, with H₂ yield of 1.61 mol H₂/mol C₂H₅OH. During the 500 h time-on-off-stream stability test, ethanol–water mixtures could be converted into H₂, CO, CH₄ and CO₂ with average selectivity values of 65.1, 17.3, 15.1 and 2.5 mol%, respectively, and average ethanol conversion values of 80.0 mol%. For the ethanol-H₂ and petrolic hybrid vehicle (EH–HV), the combustion value is the most important factor. So, it was very suitable for the EH–HV application that the low temperature ethanol steam reforming products’ distribution was with high H₂, CO, CH₄ and very low CO₂ selectivity over the special NiO/La₂O₃ flowerlike microspheres.     

Ni/CeO2 catalysts with high CO2 methanation activity and high CH4 selectivity at low temperatures

CO₂ methanation was performed over 10 wt%Ni/CeO₂, 10 wt%Ni/α-Al₂O₃, 10 wt%Ni/TiO₂, and 10 wt%Ni/MgO, and the effect of support materials on CO₂ conversion and CH₄ selectivity was examined. Catalysts were prepared by a wet impregnation method, and characterized by BET, XRD, H₂-TPR and CO₂-TPD. Ni/CeO₂ showed high CO₂ conversion especially at low temperatures compared to Ni/α-Al₂O₃, and the selectivity to CH₄ was very close to 1. The surface coverage by CO₂-derived species on CeO₂ surface and the partial reduction of CeO₂ surface could result in the high CO₂ conversion over Ni/CeO₂. In addition, superior CO methanation activity over Ni/CeO₂ led to the high CH₄ selectivity.     

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.     

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.     

Mesoporous CexMn1−xO2 composites as novel alternative carriers of supported Co3O4 catalysts for CO preferential oxidation in H2 stream

The mesoporous Co₃O₄ supported catalysts on Ce–M–O (M = Mn, Zr, Sn, Fe and Ti) composites were prepared by surfactant-assisted co-precipitation with subsequent incipient wetness impregnation (SACP–IWI) method. The catalysts were employed to eliminate trace CO from H₂-rich gases through CO preferential oxidation (CO PROX) reaction. Effects of M type in Ce–M–O support, atomic ratio of Ce/(Ce + Mn), Co₃O₄ loading and the presence of H₂O and CO₂ in feed were investigated. Among the studied Ce–M–O composites, the Ce–Mn–O is a superior carrier to the others for supported Co₃O₄ catalysts in CO PROX reaction. Co₃O₄/Ce_0.9Mn_0.1O₂ with 25 wt.% loading exhibits excellent catalytic properties and the 100% CO conversion can be achieved at 125–200 °C. Even with 10 vol.% H₂O and 10 vol.% CO₂ in feed, the complete CO transformation can still be maintained at a wide temperature range of 190–225 °C. Characterization techniques containing N₂ adsorption/desorption, X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR) and scanning electron microscopy (SEM) were employed to reveal the relationship between the nature and catalytic performance of the developed catalysts. Results show that the specific surface area doesn’t obviously affect the catalytic performance of the supported cobalt catalysts, but the right M type in carrier with appropriate amount effectively improves the Co₃O₄ dispersibility and the redox behavior of the catalysts. The large reducible Co³⁺ amount and the high tolerance to reduction atmosphere resulted from the interfacial interaction between Co₃O₄ and Ce–Mn support may significantly contribute to the high catalytic performance for CO PROX reaction, even in the simulated syngas.     

NOx emission characteristics of partially premixed laminar flames of H2/CO/CO2 mixtures

NO_x emission indices were experimentally measured for partially premixed laminar flames of five different H₂/CO/CO₂ fuels over a wide range of equivalence ratios. Through those fuels, the effects of H₂/CO ratio and CO₂ concentration on NO_x emissions, flame appearance, visible flame height and flame temperature are presented. EINO_x values increase when 1.0 ≤ Φ ≤ 1.6, then remain near the highest value, before decreasing slowly when 3.85 ≤ Φ ≤ ∞. The increase of the CO₂ concentration reduces the EINO_x for the whole range of equivalence ratios, while the increase in the H₂/CO ratio reduces the EINO_x when Φ ≤ 2.0 and is inconsequential for richer mixtures. The variation in flame temperatures approximates EINO_x trends. The variation of flame color from blue to orange when the H₂/CO ratio is increased might be explained by higher CO levels in by-product combustion.     

Enhanced ethanol steam reforming by CO2 absorption using CaO,CaO*MgO or Na2ZrO3

This paper presents results of thermodynamic analysis and experimental evaluation of hydrogen production by steam reforming of ethanol (SRE) combined with CO₂ absorption using a mixture of a solid absorbent (CaO, CaO*MgO and Na₂ZrO₃) and a Ni/Al₂O₃ catalyst. Thermodynamic analysis results indicate that a maximum of 69.5% H₂ (dry basis) is feasible at 1 atm, H₂O/C₂H₅OH = 6 (molar ratio) and T = 600 °C. whereas, the addition of a CO₂ absorbent at 1 atm, T = 600 °C and H₂O/C₂H₅OH/Absorbent = 6:1:2.5, produced a H₂ concentration of 96.6, 94.1, and 92.2% using CaO, CaO*MgO, and Na₂ZrO₃, respectively. SRE experimental evaluation achieved a maximum of 60% H₂. While combining SRE and a CO₂ absorbent exhibited a concentration of 96, 94, and 90% employing CaO, CaO*MgO, and Na₂ZrO₃, respectively at 1 atm, T = 600 °C, SV = 414 h⁻¹ and H₂O/C₂H₅OH/absorbent = 6:1:2.5 (molar ratio).     

Efficient catalytic abatement of greenhouse gases: Methane reforming with CO2 using a novel and thermally stable Rh–CeO2 catalyst

2% Rh–CeO₂ catalyst was synthesized using the hard template method and characterized by means of N₂ adsorption/desorption, XRD and H₂-TPR methods. The prepared powdered catalyst exhibited high thermal stability and high surface area with negligible sintering during 24-h exposure to 973 K in an inert atmosphere. During the temperature programmed methane dry reforming reaction between 473 and 1073 K, an increase in the molar H₂/CO ratio from 0.3 at 623 K to as high as 0.96 at 1073 K was observed. Besides H₂ and CO, H₂O was identified among reaction products, originating from the simultaneously occurring reverse water-gas shift reaction. During the isothermal test performed at 923 K, the 2% Rh–CeO₂ catalyst exhibited stable performance and produced syngas with the average H₂/CO ratio equal to 0.62. A relative drop of catalyst activity equal to 11% was observed within 70-h time on stream at 1023 K, with the average H₂/CO ratio at the reactor outlet equal to 0.71.     

Effect of Ce on 5 wt% Ni/ZSM-5 catalysts in the CO2 reforming of CH4 reaction

The aim of this study is to investigate the promotional effect of Ce on Ni/ZSM-5 catalysts in the CO₂ reforming of CH₄ reaction. The evaluation of the catalytic performances of the composite catalysts was conducted in a fixed-bed reactor at atmospheric pressure. The influencing factors, including temperature, Ni and Ce loadings, molar feed ratio of CO₂/CH₄, and time-on-stream (TOS), were investigated. The characteristics of the catalysts were checked with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The reduction and the basic properties of the composite catalysts were elucidated by temperature-programmed reduction by H₂ (H₂-TPR) and temperature-programmed desorption of CO₂ (CO₂-TPD), respectively. The reactivity of deposited carbon was studied by sequential temperature-programmed surface reaction of CH₄ (CH₄-TPSR) and temperature-programmed oxidation using CO₂ and O₂ (CO₂-TPO and O₂-TPO). Results indicate that higher CH₄ conversion, H₂ selectivity, and desired H₂/CO ratio for 5 wt% Ni & 5 wt% Ce/ZSM-5 could be achieved with CO₂/CH₄ feed ratio close to unity over the temperature range of 500–900 °C. Moreover, the addition of Ce could not only promote CH₄ decomposition for H₂ production but also the gasification of deposited carbon with CO₂. The dispersion of Ni particles could be improved with Ce presence as well. A partial reduction of CeO₂ to CeAlO₃ was observed from XPS spectra over 5 wt% Ni & 5 wt% Ce/ZSM-5 after H₂ reduction and 24 h CO₂–CH₄ reforming reaction. Benefiting from the introduction of 5 wt% Ce, the calculated apparent activation energies of CH₄ and CO₂ over the temperature range of 700–900 °C could be reduced by 30% and 40%, respectively.     

Computed flammability limits of opposed-jet H2/CO syngas diffusion flames

Extensive computations were made to determine the flammability limits of opposed-jet H₂/CO syngas diffusion flames from high stretched blowoff to low stretched quenching. Results from the U-shape extinction boundaries indicate the minimum hydrogen concentrations for H₂/CO syngas to be combustible are larger towards both ends of high strain and low strain rates. The most flammable strain rate is near one s⁻¹ where syngas diffusion flames exist with minimum 0.002% hydrogen content. The critical oxygen percentage (or limiting oxygen index) below which no diffusion flames could exist for any strain rate was found to be 4.7% for the equal-molar syngas fuels (H₂/CO = 1), and the critical oxygen percentage is lower for syngas mixture with higher hydrogen content. The flammability maps were also constructed with strain rates and pressures or dilution gases percentages as the coordinates. By adding dilution gases such as CO₂, H₂O, and N₂ to make the syngas non-flammable, besides the inert effect from the diluents, the chemical effect of H₂O contributes to higher flame temperature, while the radiation effect of H₂O and CO₂ plays an important role in the flame extinction at low strain rates.     

Solar energy powered Rankine cycle using supercritical CO2

A solar energy powered Rankine cycle using supercritical CO₂ for combined production of electricity and thermal energy is proposed. The proposed system consists of evacuated solar collectors, power generating turbine, high-temperature heat recovery system, low-temperature heat recovery system, and feed pump. The system utilizes evacuated solar collectors to convert CO₂ into high-temperature supercritical state, used to drive a turbine and thereby produce mechanical energy and hence electricity. The system also recovers heat (high-temperature heat and low-temperature heat), which could be used for refrigeration, air conditioning, hot water supply, etc. in domestic or commercial buildings. An experimental prototype has been designed and constructed. The prototype system has been tested under typical summer conditions in Kyoto, Japan; It was found that CO₂ is efficiently converted into high-temperature supercritical state, of while electricity and hot water can be generated. The experimental results show that the solar energy powered Rankine cycle using CO₂ works stably in a trans-critical region. The estimated power generation efficiency is 0.25 and heat recovery efficiency is 0.65. This study shows the potential of the application of the solar-powered Rankine cycle using supercritical CO₂.     

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.     

Enhanced H2 fermentation of organic waste by CO2 sparging

This study aimed to improve the productivity of dark fermentative hydrogen production from organic waste. An anaerobic sequencing batch reactor was used for hydrogen fermentation and it was fed with food waste (VS 4.4 ± 0.2% containing 27 g carbohydrate-COD/L) at various CO₂ sparging rates (40–120 L/L/d), hydraulic retention times (HRTs; 18–42 h), and solid retention times (SRTs; 18–160 h). CO₂ sparging increased the H₂ productivity by 5–36% at all the examined conditions, confirming the benefit of the replacement of headspace gas by CO₂. The maximum H₂ production was obtained by CO₂ sparging at 80 L/L/d, resulting in the H₂ productivity of 3.18 L H₂/L/d and the H₂ yield of 97.3 mL H₂/g VS_added. Increase of n-butyrate and isopropanol yields were concurrent with the enhanced H₂ yield by CO₂ sparging. Acidogenic efficiency, the sum of H₂, organic acid, and alcohol, in the CO₂-sparged reactor ranged from 47.9 to 56.0%, which was comparable to conventional acidogenesis. Thermodynamic analysis confirmed that both CO₂ sparging and CO₂ removal were beneficial for H₂-producing reactions, but CO₂ sparing has more profound effect than CO₂ removal on inhibiting H₂-consuming reactions.     

Coal gasification by CO2 gas bubbling in molten salt for solar/fossil energy hybridization

Coal gasification with CO₂ (the Boudouard reaction: C+CO₂=2CO, Δ_rH°=169.2 kJ/mol at 1150 K), which can be applied to a solar thermochemical process to convert concentrated solar heat into chemical energy, was conducted in the molten salt medium (eutectic mixture of Na₂CO₃ and K₂CO₃, weight ratio=1/1) to provide thermal storage. When CO₂ gas was bubbled through the molten salt, higher reaction rates were observed compared to the case without CO₂ gas bubbling (CO₂ gas was streamed over the surface of the molten salt). Thus the coke formed by coal pyrolysis was well suspended in the molten salt by CO₂ gas bubbling. When the CO₂ flow rate was increased from 15 to 60 μmol/s, the CO evolution rate was increased (15 to 26 μmol/s). However, CO₂ conversion efficiency was decreased (50 to 22%). Based on the maximum CO evolution rate (26 μmol/s), solar thermal energy from a solar farm (300×300 m²) could be converted to chemical energy at a rate of 50,000 kJ/s by the coal (23 ton as C) gasification process studied here. This assumes 50% solar heat to chemical energy conversion efficiency which can be generally obtained by the actual solar experiments.     

Investigation of novel mixed metal ferrites for pure H2 and CO2 production using chemical looping

The mixed metal oxides NiFe₂O₄ and CoFe₂O₄ are candidate materials for the Chemical Looping Hydrogen (CLH) process, which produces pure and separate streams of H₂ and CO₂ without the use of complicated and expensive separations equipment. In the CLH process, syngas reduces a metal oxide, oxidizing the H₂ and CO in the syngas to H₂O and CO₂, and “stores” the chemical energy of the syngas in the reduced metal oxide. The reduced metal oxide is then oxidized in steam to regenerate the original metal oxide and produce H₂. In this study, we report thermodynamic modeling and experimental results regarding the syngas reduction and H₂O oxidation of NiFe₂O₄ and CoFe₂O₄ to determine the feasibility of their use in the CLH process. Modeling predicts the oxidation of nearly all the CO and H₂ in syngas to H₂O and CO₂ during the reduction step for both materials, and regeneration of the mixed metal spinel phase during oxidation with excess H₂O. Laboratory tests in a packed bed reactor confirmed over 99% conversion of H₂ and CO to H₂O and CO₂ during reduction of NiFe₂O₄ and CoFe₂O₄. Powder XRD analysis of the reduced materials showed, in accordance with thermodynamic predictions, the presence of a spinel phase and a metallic phase. High reactivity of the reduced NiFe₂O₄ and CoFe₂O₄ with H₂O was observed, and XRD analysis confirmed re-oxidation to NiFe₂O₄ and CoFe₂O₄ under the conditions tested. When compared with a conventional Fe-based CLH material, the mixed metal spinels showed a higher extent of reduction under the same conditions, and produced four times the H₂ per mass of active material than the Fe-based material. Analysis of the H₂ and CO consumed in the reduction and the H₂ produced during the oxidation showed over 90% conversion of the H₂ and CO in syngas back to H₂ during oxidation.