Modeling of a continuous photocatalytic reactor for isovaleraldehyde oxidation: Effect of different operating parameters and chemical degradation pathway

An investigation of isovaleraldehyde (ISOV) photocatalytic oxidation was conducted at initial concentrations ranging from 25 to 150 mg/m³ and different relative humidities (5–90% RH) in order to characterize the process performances close to indoor air conditions. Experiments were carried out in two different reactors: cylinder and flat-plate photoreactor (planar reactor) at different air gap (20–60 mm) and gas residence times (0.67–5.0 s). A plug flow reactor system was developed in order to perform kinetic studies of (i) isovaleraldehyde removal, (ii) selectivity of CO₂, (iii) by-products formation and removal. It appears that ISOV removal efficiencies increased with lower inlet concentrations, lower air gap and higher gas residence times.     

Electrochemical decomposition of CO2 and CO gases using porous yttria-stabilized zirconia cell

Electrochemical decomposition of CO₂ and CO gases using a porous cell of Ru-8 mol% yttria-stabilized zirconia (YSZ) anode/porous YSZ electrolyte/Ni–YSZ cathode system at 400–800 °C was studied by analyzing the flow rate and composition of outlet gas, current density, and phases and elementary distribution of the electrodes and electrolyte. A part of CO₂ gas supplied at 50 ml/min was decomposed to solid carbon and O₂ gas through the cell at the electric field strengths of 0.9–1.0 V/cm. The outlet gas at a flow rate of 3 ml/min included 61–63% CO₂ and 37–39% O₂ at 700–800 °C and the outlet gas at a flow rate of 50 ml/min included 73–96% (average 85%) CO₂ and 4–27% (average 15%) O₂ at 800 °C. On the other hand, the supplied CO gas was also decomposed to solid carbon, O₂ and CO₂ gases at 800 °C. The fraction of outlet gas at a flow rate of 50 ml/min during the CO decomposition at 800 °C for 5 h was 11–36% CO, 59–81% O₂ and 2–9% CO₂. The detailed decomposition mechanisms of CO₂ and CO gases are discussed. Both Ni metal in the cathode and porous YSZ grains under the DC electric field have the ability to decompose CO gas into solid carbon and O²⁻ ions or O₂ gas.     

Performance evaluation under supercritical conditions of Fe–Mn–Cu–K composite catalysts synthesized by supercritical methods

A series of nanosized Fe–Mn–Cu–K composite catalysts was prepared by a supercritical combined technology. The nanosized catalysts were characterized by means of XRD, TEM and BET techniques, and tested for catalytic performance under Fischer–Tropsch synthesis (FTS) reaction conditions. The catalyst synthesized by the supercritical combined technology has some excellent properties. Additionally, the drying and crystallization of nanosize catalyst could be achieved simultaneously by this supercritical combined technology. The addition of Mn, Cu and K promoters can improve the catalytic performance properties of the catalyst, including lower CH₄ and CO₂ formation rates, and higher production rates of desired light-olefin. The optimal performance with a 95.7% CO conversion and a 46.5% light-olefin yield was obtained by using a catalyst component of Fe/Mn/Cu/K = 60:25:10:8.5. In summary, optimal catalytic performance was obtained by using the nanosized catalyst under supercritical reaction conditions, resulting in higher CO conversion, less byproduct CO₂ formation, and a higher yield of light-olefin.     

Comparative study of CO and CO2 hydrogenation over supported Rh–Fe catalysts

The hydrogenation of CO, CO + CO₂, and CO₂ over titania-supported Rh, Rh–Fe, and Fe catalysts was carried out in a fixed-bed micro-reactor system nominally operating at 543 K, 20 atm, 20 cm³ min^− 1 gas flow (corresponding to a weight hourly space velocity (WHSV) of 8000 cm³ g_cat^− 1 h^− 1), with a H₂:(CO + CO₂) ratio of 1:1. A comparative study of CO and CO₂ hydrogenation shows that while Rh and Rh–Fe/TiO₂ catalysts exhibited appreciable selectivity to ethanol during CO hydrogenation, they functioned primarily as methanation catalysts during CO₂ hydrogenation. The Fe/TiO₂ sample was primarily a reverse water gas shift catalyst. Higher reaction temperatures favored methane formation over alcohol synthesis and reverse water gas shift. The effect of pressure was not significant over the range of 10 to 20 atm.     

Effect of gas pressure on the phase behaviour of organometallic compounds

The knowledge of the phase behaviour of organometallic compounds in supercritical CO₂ is the key factor for determining the feasibility of homogeneous catalysis in supercritical fluid reaction. In the present study, the solid-liquid-gas equilibrium line for the system CO₂/Cu(thd)₂, CO₂/Pt(COD)Me₂ and He/Pt(COD)Me₂ was determined from 0.1 MPa to 25 MPa. In addition, experimental solubility data of Cu(thd)₂ in CO₂ at 333 K and pressures ranging from 10 MPa to 17 MPa as well as of Pt(COD)Me₂ in CO2 at 313 K, 333 K and 353 K and pressures ranging from 12 MPa to 32 MPa are presented. The solubility data are correlated using the linear relationship between the logarithm of the solubility and the logarithm of the reduced density of pure CO₂ proposed by Kumar and Johnston as well as an extension of the theory of dilute solution proposed by Mendez-Santiago and Teja. Both approaches gave reasonable results in the correlation of the experimental solubility data.     

Analysis of the scale up of a transpiring wall reactor with a hydrothermal flame as a heat source for the supercritical water oxidation

Experimental data from a tubular reactor and from a transpiring wall reactor (TWR) are used to analyze the scaling up of SCWO reactors operating with a hydrothermal flame as a heat source. Results obtained with the tubular reactor show that fluid velocity inside the reactor determines the minimum injection temperature at which a stable hydrothermal flame is formed. When the fluid velocity inside of the reactor is lower, the extinction temperature of the hydrothermal flame in that reactor is also lower. Using this reactor, extinction temperatures are always near or above the critical temperature of water. Total TOC removals are possible working with isopropyl-alcohol at temperatures between 650 and 700 °C and residence times of 0.5 s. Results of the TWR show that steady operation with a hydrothermal flame inside is possible even when reagents are injected at subcritical conditions as low as 170 °C. Temperature measurements show that reaction is not initiated in the injector but in the reaction chamber, where fluid velocity is lower than 0.1 s. This was explained by estimating that the flame front velocity of a hydrothermal flame is of the order of 0.1 m/s. Thus, it is expected that the flame is stabilized in the reaction chamber and not in the injector, where fluid velocities are higher than 2 m/s. A previously developed model of the TWR was modified in order to describe the ignition in the reaction chamber and not in the injector. The model reproduces satisfactorily experimental data and it was used to propose the design of scaled up reactors for SCWO with a hydrothermal flame inside.     

Experimental study on sawdust air gasification in an entrained-flow reactor

Experiments were performed in an entrained-flow reactor to better understand the processes involved in biomass air gasification. Effects of the reaction temperatures (700 °C, 800 °C, 900 °C and 1000 °C), residence time and the equivalence ratio in the range of 0.22-0.34 on the gasification process were investigated. The behavior of biomass gasification was discussed in terms of composition of produced gas. Four parameters, i.e. the low heating value, fuel gas production, carbon conversion and cold gas efficiency were used to evaluate the gasification. The results show that CO, CO₂ and H₂ are the main gasification products, while hydrocarbons (CH₄ and C₂H₄) are the minor ones. With the increase of the reaction temperature, the concentration of CO decreases, while the concentrations of CO₂ and H₂ increase. The concentrations of CH₄ and C₂H₄ reach their maximum value when the reaction temperature is 800 °C. The optimal reaction temperature is considered to be 800 °C and the optimal equivalence ratio is 0.28 in that the low heating value of the produced gas, carbon conversion and cold gas efficiency achieve their maximum values. The kinetic parameters of sawdust air gasification are calculated basing on the Arrhenius correlation.     

Hydrogen production by oxidative steam reforming of methanol using ceria promoted copper–alumina catalysts

The performance of different Cu/CeO₂/Al₂O₃ catalysts of varying compositions is investigated for the oxidative steam reforming of methanol (OSRM) in order to produce the hydrogen selectively for polymer electrolyte membrane (PEM) fuel cell applications. All the catalysts were prepared by co-precipitation method and characterized for their surface area, pore volume and oxidation–reduction behavior. The effect of various operating parameters studied are as follows: reaction temperature (200–300 °C), contact-time (W/F = 3–15 kg_cat s mol^− 1) and oxygen to methanol (O/M) molar ratio (0–0.5). The steam to methanol (S/M) molar ratio = 1.5 and pressure = 1 atm were kept constant. Among all the catalysts studied, catalyst Cu–Ce–Al:30–20–50 exhibited 100% methanol conversion and 179 mmol s^− 1 kg_cat^− 1 hydrogen production rate at 280 °C with carbon monoxide formation as low as 0.19%. The high catalytic activity and hydrogen selectivity shown by ceria promoted Cu/Al₂O₃ catalysts is attributed to the improved specific surface area, dispersion and reducibility of copper which were confirmed by characterizing the catalysts through temperature programmed reduction (TPR), CO chemisorption, X-ray diffraction (XRD) and N₂ adsorption–desorption studies. Reaction parameters were optimized in order to produce hydrogen with carbon monoxide formation as low as possible. The time-on-stream stability test showed that the Cu/CeO₂/Al₂O₃ catalysts were quite stable.     

Effects of specific adsorption of copper (II) ion on charge transfer reaction at the thin film LiMn2O4 electrode/aqueous electrolyte interface

This study investigated the effect of a specific adsorption ion, copper (II) ion, on the kinetics of the charge transfer reaction at a LiMn₂O₄ thin film electrode/aqueous solution (1 mol dm⁻³ LiNO₃) interface. The zeta potential of LiMn₂O₄ particles showed a negative value in 1 × 10⁻² mol dm⁻³ LiNO₃ aqueous solution, while it was measured as positive in the presence of 1 × 10⁻² mol dm⁻³ Cu(NO₃)₂ in the solution. The presence of copper (II) ions in the solution increased the charge transfer resistance, and CV measurement revealed that the lithium insertion/extraction reaction was retarded by the presence of small amount of copper (II) ions. The activation energy for the charge transfer reaction in the solution with Cu(NO₃)₂ was estimated to be 35 kJ mol⁻¹, which was ca. 10 kJ mol⁻¹ larger than that observed in the solution without Cu(NO₃)₂. These results suggest that the interaction between the lithium ion and electrode surface is a factor in the kinetics of charge transfer reaction.     

Supercritical water oxidation of coal: Investigation of operating parameters' effects, reaction kinetics and mechanism

Supercritical water oxidation (SCWO) of coal was conducted in a continuous tubular reactor under various reaction conditions. Our experimental results show that the removal rate of chemical oxygen demand (COD) had no significant dependence on the temperature variations. Effect of residence time was less significant as exceeded fixed values. Free radical mechanism of SCWO reaction may be a possible explanation for the relative low conversion rate of coal at the range of tested oxygen excess. Compared with other parameters, effect of pressure was less significant. A global power-law rate expression was regressed from experimental data. The reaction orders for coal slurry and oxidant were 1.79 and 0.28 respectively. The reaction activation energy E_a was determined to be 112.3 kJ mol⁻¹, and the pre-exponential factor k₀ was 412 (mol/L)^−1.07 s⁻¹. The deviation between the model and experimental data was within ± 9%. Free radical mechanism, oxidation and hydrolysis mechanisms and phenolic hydroxyl oxidation mechanism were considered to be the possible mechanisms for the SCWO process of coal.     

Influence of the calcination on the activity and stability of the Cu/ZnO/Al2O3 catalyst in liquid phase methanol synthesis

Catalyst Cu/ZnO/Al₂O₃ was prepared through co-precipitation method and investigated in a stirred slurry autoclave reactor system for methanol synthesis. The structure of the catalysts was studied by derivative thermogravimetry (DTG), X-ray diffraction (XRD) and H₂ temperature programmed reduction (H₂-TPR). The results show that the average size of CuO crystallite of the catalyst was 3.23 nm when the catalyst was calcined at 623 K for 2.0 h, and the catalyst with this size of CuO crystallite is highly active and stable. Its space time yield and deactivation rate reached 172.2 g/kg_cat·h and 0.43%/d, respectively under the reaction conditions of 513 K, 4.0 MPa, H₂/CO/CO₂ = 68/24/5 and space velocity = 810 ml/g_cat·h.     

Pyrolysis of wood at high temperature: The influence of experimental parameters on gaseous products

The pyrolysis of wood was carried out in an Entrained Flow Reactor at high temperature (650 to 950 °C) and under rapid heating conditions (> 10³ K s^− 1). The influence of the diameter and initial moisture of the particle, reactor temperature, residence time and the nature of the gaseous atmosphere on the composition of the gaseous products has been characterised. Particle size, between 80-125 and 160-200 μm, did not show any impact. Pyrolysis and tar cracking essentially happen in very short time period: less than 0.6 s; the products yields are only slightly modified after 0.6 s in the short residence times (several seconds) of our experiments. Higher temperatures improve hydrogen yield in the gaseous product while CO yield decreases. Under nitrogen atmosphere, after 2 s at 950 °C, 76% (daf) of the mass of wood is recovered as gases: CO, CO₂, H₂, CH₄, C₂H₂, C₂H₄ and H₂O. Tests performed under steam partial pressure showed that hydrogen production is slightly enhanced.     

A novel nickel/carbon catalyst for CH4 and H2 production from organic compounds dissolved in wastewater by catalytic hydrothermal gasification

A novel Ni/carbon catalyst recently developed by the authors was used to gasify organic compounds dissolved in the wastewater with TOC concentration from 0.2 to 2%. The process removes the organic compounds by gasifying them into high calorific gases like methane and hydrogen. The investigations were focused on the efficiency of the Ni/carbon catalyst in terms of carbon conversion, conversion of big organic molecules, and catalyst deactivation due to sintering. The preliminary results showed that up to 99% carbon conversion can be achieved at 360 °C, and 20 MPa. A conversion mechanism was suggested which consists of: first, decomposition of big molecules to small molecules on the metal surface, steam gasification of small molecules to produce CO and H₂ followed by CO methanation and CO shift reaction to produce CH₄ and CO₂. The catalyst was found to be highly active and stable and no sintering was observed even after 100 h of reaction time.     

Comparison of natural ilmenites as oxygen carriers in chemical-looping combustion and influence of water gas shift reaction on gas composition

Chemical-looping combustion (CLC) is a promising technology for CO₂-capture for storage or reuse as a method to mitigate CO₂ emissions from the use of fossil fuels. In a CLC system the oxygen carrier is of great importance. Environmentally sound and low cost materials seem to be preferable especially for CLC of solid fuels. The natural occurring ore ilmenite has already been the target of different studies in order to work out its feasibility as oxygen carrier for different fuels. The initial part of this work is a screening of five commercial available ilmenite minerals as oxygen carrier, crushed and sieved to 125–180 μm. The screening includes an examination of the sulfur released during the first heat up and the activation of the oxygen carrier, indicated by the fuel conversion using alternating reduction (syngas 50 vol.% CO in H₂) and oxidation conditions (10 vol.% O₂ in N₂). The five first cycles were carried out at 850 °C to avoid initial agglomeration whereas the main activation cycles have been performed at 950 °C in a tubular quartz reactor under fluidized bed conditions. From these experiments it is concluded that rock ilmenites are preferable as oxygen carriers since they revealed an improved fuel conversion, although offering a higher sulfur content, which is released during the initial heat up.     

Influence of process parameters on the hydrothermal decomposition and oxidation of glucose in sub- and supercritical water

Supercritical water oxidation (SCWO) of wet waste biomass for energy recovery could be an advantageous alternative to conventional combustion with preceding drying. Therefore the reactions of glucose as a model substance for cellulosic biomass were investigated in sub- and supercritical water. The results of hydrothermal and oxidative experiments carried out in a continuous high-pressure plant with a feed solution of 0.2-1.2% (g g⁻¹) glucose at 24-34 MPa, 250-480 °C and residence times of 2-35 s are presented. In the presence of a stoichiometric oxygen concentration (for total oxidation to carbon dioxide and water) glucose decomposes already at subcritical temperatures readily to carbon monoxide and low molecular liquid substances, chiefly organic acids like e.g. acetic acid and glycolic acid. In turn these are in general more stable and react only slowly with oxygen. The effect of temperature, residence time, pressure, reactant concentration and addition of zinc sulfate on the conversion and the yields of reaction products was demonstrated. Already at 350 °C (24 MPa and 30 s) 99% of the glucose are converted. With increasing temperature the production of CO₂ increases. However, even at 480 °C (34 MPa and 4 s) significant amounts of CO are formed and the reaction of glucose to CO₂ and H₂O is not complete. Higher temperatures or greatly longer residence times are needed for a total combustion of the glucose.     

Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction

The influence of poisoning of Pt catalyst by CO on the kinetics and mechanism of H₂ oxidation reaction (HOR) at Pt/C electrode in 0.5 mol dm⁻³ HClO₄, saturated with H₂ containing 100 ppm CO, was examined with rotating disc electrode (RDE) at 22 °C. Commercial carbon black, Vulcan XC-72 was used as support, while Pt/C catalyst was prepared by modified polyol synthesis method in an ethylene glycol (EG) solution. The kinetically controlled current (I_k) for the HOR at Pt/C decreases significantly at CO coverage (Θ_CO) > 0.6. For Θ_CO < 0.6 the HOR takes place through Tafel-Volmer mechanism with Tafel reaction as rate-determining step at the low CO coverage, while Volmer step controls the overall reaction rate at the medium CO coverage. When CO coverage is higher then 0.6, Heyrovsky-Volmer mechanism is operative for the HOR with Heyrovsky as the rate-determining step (rds).     

The process design and simulation for the methanol production on the FPSO (floating production,storage and off-loading) system

A process for methanol production from 100 MM scfd of stranded gas and CO₂ is proposed and simulated using a commercial process simulator, PRO/II v.9.1, for a FPSO (floating production, storage, off-loading) system. The process consists of Steam-CO₂ Reforming (SCR), methanol synthesis, a Reverse Water-Gas Shift (RWGS) reaction and ancillaries with recycle streams to SCR and RWGS. All reactors were simulated using the Gibbs reactor model. Also, the Plug Flow Reactor (PFR) model with reaction rate equations was used for the methanol reactor and the result was compared to the Gibbs reactor model. To maximize the use of the carbon source in stranded gas and CO₂ while avoiding an undesirable increase in process size, the optimum recycle ratios were calculated with a satisfying constraint, a steam-to-carbon ratio ≥ 1 in the SCR. In the proposed Methanol-FPSO process the RWGS reactor can maximize CO₂ utilization and case studies were performed to analyze the influence of RWGS.     

Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.     

Investigating the effect of metal oxide additives on the properties of Cu/ZnO/Al2O3 catalysts in methanol synthesis from syngas using factorial experimental design

The Cu/ZnO/Al₂O₃ catalysts, prepared by co-precipitation method, have been modified by adding small amount of Mn, Mg, Zr, Cr, Ba, W and Ce oxides using design of experiments (1/16 full factorial design). The structure and morphology of catalysts were studied by X-ray diffraction (XRD) and BET. Performance of the prepared catalysts for CO/CO₂ hydrogenation to methanol was evaluated by using a stainless steel fixed-bed reactor at 5 MPa and 513 K. The oxide additives were found to influence the catalytic activity, dispersion of Cu, Cu crystallite size, surface composition of catalyst and stability of catalysts during their operations. The results showed that the Mn and Zr promoted catalysts have high performance for methanol synthesis from syngas.     

Experimental studies and modeling of a fixed bed reactor for Fischer-Tropsch synthesis using biosyngas

The aim of this work was to study the Fischer-Tropsch (FT) synthesis of a model biosyngas (33% H₂, 17% CO and 50% N₂) in a single tube fixed-bed FT reactor. The FT reactor consisted of a shell and tube with high-pressure boiling water circulating throughout the shell. A spherical unpromoted cobalt catalyst was used with the following reaction conditions: a wall temperature of 473 K, a pressure of 20 bars and a gas hour space velocity (GHSV) of 37 to 180 NmL.g_cat^− 1.h^− 1. The performance of the FT reactor was also validated by developing a 2D pseudo-homogeneous model that includes transport equations and reaction rate equations. Good agreement between the model predictions and experimental results were obtained. This developed model was extended to predict and quantify the influence of the FT kinetics as well as determine the influence of the tube diameter and the wall temperature. The predicted behaviors for CO and H₂ conversion, productivity of hydrocarbons (mainly CH₄ and C₅₊) and fluid temperature along the axis of the reactor have been analyzed.