Scale-up and optimization of a two-stage molten salt oxidation reactor system for the treatment of cation exchange resins

A prototype two-stage MSO (molten salt oxidation) reactor system with a capacity of 10 kg/h was developed based on the test results of lab-scale and bench-scale MSO systems. This study first discusses the features of the prototype MSO reactor system. The second part of the study attempts to identify the proper conditions of the prototype two-stage MSO reactor system, where each reactor performs different functions. The volatility of radioactive elements doped in the spent resins was first investigated to establish the proper operating conditions of the primary MSO reactor. A parametric model study of the secondary MSO reactor for the oxidation of hydrocarbons from the primary reactor and an experimental validation were then performed to establish the optimum conditions for the two-stage MSO reactor system. The retention of cesium was greatly influenced by the pyrolysis temperature. The highest pyrolysis temperature with cesium retention of ≥99.9% was 790 °C and this was established as the optimum primary reactor temperature. The optimum conditions of secondary MSO reactor for the substantial oxidation of hydrocarbons generated from the primary MSO reactor were determined to be λ (the ratio of actual air feed rate per stoichiometric air rate) of 2, and a temperature of 800 °C.     

The effect of temperature on the adiabatic laminar burning velocities of CH4−air and H2−air flames

The effect of temperature on the adiabatic laminar burning velocities of CH₄ + air and H₂ + air flames was analyzed. Available measurements were interpreted using correlation S_L = S_L0 (T/T₀)^α. Particular attention was paid to the variation of the power exponent α with equivalence ratio at fixed (atmospheric) pressure. Experimental data and proposed empirical expressions for α as a function of equivalence ratio were summarized. They were compared with predictions of detailed kinetic models in methane + air and hydrogen + air flames. Unexpected non-monotonic behavior of α was found in rich methane + air flames. Modeling results are further examined using sensitivity analysis to elucidate the reason of particular dependences of the power exponent α on equivalence ratio.     

Syngas and a separate nitrogen/argon stream via chemical looping reforming - A 140 kW pilot plant study

A dual circulating fluidized bed pilot plant was operated in chemical looping reforming conditions at a scale of 140 kW fuel power with natural gas as fuel. A nickel-based oxygen carrier was used as bed material. The pilot plant is equipped with an adjustable cooling system. Three experimental campaigns have been carried out at 747 °C (1020 K), 798 °C (1071 K) and 903 °C (1176 K), respectively. In each campaign, the global stoichiometric air/fuel ratio was varied step-wise between 1.1 and the minimum value possible to keep the desired operating temperature when the cooling is finally switched off. The results show that the fuel reactor exhaust gas approaches thermodynamic equilibrium. The residual amount of methane left decreases with increasing fuel reactor temperature. Further, the oxygen in the air reactor can be completely absorbed by the solids as soon as the air reactor operating temperature is higher than 900 °C (1173 K). Even though no steam was added to the natural gas feed no carbon formation was found for global excess air ratios larger than 0.4.     

Laminar burning velocities of n-heptane, iso-octane, ethanol and their binary and tertiary mixtures

Measurements of the adiabatic laminar burning velocities of n-heptane, iso-octane, ethanol and their binary and tertiary mixtures are reported. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss from the flame to the burner is zero. Initial temperatures of the gas mixtures with air were 298 and 338 K. Uncertainties of the measurements were analyzed and assessed experimentally. The overall accuracy of the burning velocities was estimated to be better than ±1 cm/s. These new measurements were compared with the literature data when available. Experimental results in lean ethanol + air mixtures are systematically higher than previous measurements under similar conditions. Good agreement for n-heptane + air flames and for iso-octane + air flames was found with the experiments performed in counter-flow twin flames with linear extrapolation to zero stretch.     

Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor

This work investigates the production of fatty acid ethyl esters (FAEEs) from the transesterification of soybean oil in supercritical ethanol in a continuous catalyst-free process. Experiments were performed in a microtube reactor in the temperature range of 523 K to 598 K, from 10 MPa to 20 MPa, varying the oil to ethanol molar ratio from 1:10 to 1:40, and evaluating the effects of addition of carbon dioxide as co-solvent. Results showed that ethyl esters yield obtained in the microtube reactor (inner diameter 0.76 mm) were higher than those obtained in a tubular reactor (inner diameter 3.2 mm) possibly due to improved mass-transfer conditions attained inside the microtube reactor. Non-negligible reaction yields (70 wt.%) were achieved along with low total decomposition of fatty acids (< 5.0 wt.%). It is shown that the use of carbon dioxide as co-solvent in the proposed microtube reactor did not significantly affect the ethyl esters yield within the experimental variable ranges investigated.     

Adiabatic laminar burning velocities of CH4 + H2 + air flames at low pressures

Experimental measurements of the adiabatic burning velocity in methane + hydrogen + air flames using the Heat Flux method are presented. The hydrogen content in the fuel was varied from 0 to 20%. Non-stretched flames were stabilized on a perforated plate burner from 20 to 100 kPa. The equivalence ratio was varied from 0.8 to 1.4. Adiabatic burning velocities of CH₄ + H₂ + air mixtures were found in good agreement with the literature results at atmospheric pressure. Also low-pressure measurements in CH₄ + air flames performed earlier were accurately reproduced. The effects of enrichment by hydrogen on the laminar burning velocity at low pressures have been studied for the first time. Calculated burning velocities using the Konnov mechanism are in satisfactory agreement with the experiments over the entire range of conditions. Pressure dependences of the burning velocities for the three fuels studied could be approximated by an empirical exponential correlation.     

Interactions of CO, HCl, and SOx in pulverised coal flames

The effect of HCl and SO₂ on CO oxidation in pulverised coal flames was investigated experimentally and kinetically in an entrained flow combustion reactor. Two bituminous coals (German ‘Goettelborn’ and a Polish coal) were used as fuels with a feeding rate of 1 or 1.5 kg/h. HCl or SO₂ is introduced into the reactor premixed with the primary air. Experimental results indicate that HCl addition may inhibit CO oxidation in coal flames and increases CO emission. Reducing temperature in the reactor will enhance the inhibitory effect of HCl on CO oxidation. The measured CO profiles along the reactor height clearly show that the addition of HCl may inhibit CO oxidation. In the experimental range of SO₂ addition, the inhibiting effect of SO₂ on CO oxidation is less significant than HCl. A detailed kinetic mechanism is used to model the reactions, and the controlling reactions are analysed.     

Wet air oxidation of polyether solutions

This paper studied the characteristics of wet air oxidation (WAO) on polyether as non-ionic surfactant and analyzed its main intermediates. The results showed that, WAO was an effective method to treat non-ionic surfactants like polyether; temperature played a decisive role throughout the process: the COD removal percentage within 2 h was only 33.5% at 160 °C, 57.2% at 200 °C, and 94.4% at 240; fatty acid was the major intermediate, and oxidation of acetic acid was the key rate-determining step during fatty acid oxidation, and the oxidation of fatty acid could be accelerated by rising the temperature as well as elongating the reaction time. Meanwhile, oxidative decomposition of polyether and oxidation on fatty acid were the rate-determining steps to the whole WAO process, the oxidation of polyether was relatively more limited at lower temperature; on the contrary, the oxidation of fatty acid and other organics was obviously more limited at higher temperature.     

Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 °C and 700 °C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 °C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H₂O₂/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 °C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed.     

Forced temperature cycling of a catalyst layer and its application to propylene oxidation

In this study, a new reaction device suited for forced temperature cycling was developed. This device has a heating element in the reaction tube, and forced temperature cycling was realized by operating this element intermittently. The energy needed for the operation was about 20 W, which is much less than that required to operate reactors used in previous studies of temperature cycling. This reactor was used to examine the effect of periodic operation on the oxidation of propylene. It was found that the conversion under periodic conditions was higher than that observed under steady state. In addition, the reaction system approached a relaxed steady state as the cycle time was reduced to 1 s. The effect of forced temperature cycling on propylene oxidation was successfully demonstrated.     

Chemical-looping with oxygen uncoupling using CuO/ZrO2 with petroleum coke

Oxygen carrier particles of CuO/ZrO₂ were reacted with petroleum coke using chemical-looping with oxygen uncoupling (CLOU). The fuel was burnt in gas-phase oxygen released from the oxygen carrier particles during the fuel oxidation. The particles were then regenerated in 5-21% oxygen. In this process, the carbon dioxide from the combustion is inherently separated from the rest of the flue gases without the need for an energy intensive air separation unit. Copper oxide has thermodynamic characteristics that make it suitable as an oxygen carrier in CLOU. Particles were prepared by freeze granulation and were exposed cyclically with petroleum coke and oxygen in a laboratory fluidized bed reactor of quartz. The reaction temperature and oxygen concentration during the oxidation were varied. The average conversion rate of petroleum coke was a function of temperature and varied between 0.5%/s and 5%/s in the set-point temperature interval 885-985 °C. The conversion rate is considerably higher than rates obtained with the same fuel using iron-based oxygen-carrier in chemical-looping combustion. As for the regeneration with oxygen, the reduced particles reacted at low oxygen concentrations, with a considerable part of the reaction occurring near the thermodynamic equilibrium.     

Effect of gas feed flow and gas composition modulation on activated carbon performance in phenol wet air oxidation

Modulation of gas feed composition (air/N₂ cycling) and gas feed flow (on-off air cycling) was investigated in the catalytic wet air oxidation of phenol over activated carbon (AC). Fifty hours lasting experiments were conducted in a laboratory trickle bed reactor at 140-160 °C, 2 bar of oxygen partial pressure and different splits and periods to determine the set of cycling parameters that optimise the periodic reactor operation. To follow the dynamic behaviour of the phenol oxidation, temperature and conversion were continuously monitored by means of computerised data acquisition and automatic liquid sampling. Several long term tests over 144 h were also run using both periodic operating strategies to compare the activity and stability of AC with those obtained in a steady state operation at otherwise same conditions. The results show that, depending on the selection of split and period, modulation of the gas phase significantly improves the stability of AC compared to steady state operation, thereby performing a superior long term phenol conversion.     

Selectivity engineering in the synthesis of value added chemicals: Oxidation of 1-octanol to 1-octanal over nano-fibrous Ag-OMS-2 catalysts

Oxidation of 1-octanol to 1-octanal is commercially very attractive, since the product is used extensively in the fragrance industry. Among the various methods, selective air oxidation with a suitable heterogeneous catalyst will be green and clean. In this work, novel cryptomelane type octahedral molecular sieve type 2 (Ag-OMS-2) catalysts, with Ag loading from 5 to 15%, w/w, were synthesized and evaluated in air oxidation of 1-octanol in a fixed bed vapour phase reactor. All catalysts were fully characterized to understand the activity and selectivity. The conversion increased with Ag loading but the selectivity was the highest for 10% Ag-OMS-2. A systematic study was conducted to ascertain the effects of various parameters. Use of toluene as a diluant leads to better conversion and selectivity. The optimized conditions are: catalyst mass/molar flow rate of 1-octanol (W/F_A0)- 20 g h/mol, 523 K, toluene to 1-octanol molar ratio- 4:1, weight hourly space velocity (WHSV)- 16.74 h⁻¹, air flow rate- 6 L/h, air pressure- 101.3 kPa. It follows the Mars-van Krevelen mechanism and is intrinsically kinetically controlled. The activation energy is 14.39 kcal/mol using 10%, w/w Ag-OMS-2. It provides a better green process than those reported so far.     

Hydrogen production from oxidative steam reforming of ethanol in a palladium-silver alloy composite membrane reactor

In this investigation, we studied the oxidative steam reforming reaction of ethanol in a Pd-Ag/PSS membrane reactor for the production of high purity hydrogen. Palladium and silver were deposited on porous stainless steel (PSS) tube via the sequential electroless plating procedure with an overall film thickness of 20 μm and Pd/Ag weight ratio of 78/22. An ethanol-water mixture (n_water/n_ethanol = 1 or 3) and oxygen (n_oxygen/n_ethanol = 0.2, 0.7 or 1.0) were fed concurrently into the membrane reactor packed with Zn-Cu commercial catalyst (MDC-3). The reaction temperatures were set at 593-723 K and the pressures at 3-10 atm. The hydrogen flux in the permeation side increased proportionately with increasing pressure; however, it reduced slightly when increasing oxygen input. This is probably due to the fast oxidation reaction that consumes hydrogen before the onset of the steam reforming reaction. The effect of oxygen plays a vital role on the ethanol oxidation steam reforming reaction, especially for a Pd-Ag membrane reactor in which a higher flux of hydrogen is required. The selectivity of CO₂ increased with increasing flow rate of oxygen, while the selectivity of CO remained almost the same.     

Transesterification of sunflower oil in a countercurrent trickle-bed reactor packed with a CaO catalyst

Transesterification of sunflower oil with methanol to form biodiesel was performed in a countercurrent trickle-bed reactor, using calcium oxide particles 1-2 mm in diameter as a packed, solid base catalyst. Although biodiesel production generally requires a reaction temperature below the boiling point of methanol to maintain a heterogeneous, liquid-liquid reaction, in the present study the reaction temperature was varied from 80 to 140 °C to confirm the progress of transesterification in a gas-liquid-solid phase reaction system. Oil droplets released from a thin tube flowed downward, while vaporized methanol flowed upward in the bed. The effects of the reaction temperature, methanol and oil flow rates, and the bed height on the FAME yield were investigated. The oil residence time in the reactor, which was controlled by changing both the oil flow rate and the bed height, had a significant effect on the FAME yield. In addition, the FAME yield increased with reaction temperature and was maximal at 373 K due to the change in residence time associated with reduced oil viscosity at higher temperatures. The FAME yield was 98% at a reaction temperature of 373 K when the methanol and oil flow rates were 3.8 and 4.1 mL/h, respectively.     

Flame length scaling in a non-premixed turbulent diluted hydrogen jet with coaxial air

The effect of fuel composition on flame length was studied in a non-premixed turbulent diluted hydrogen jet with coaxial air. Because coaxial air entrained in a fuel stream enhances the mixing rate of fuel and air, it substantially reduces flame length. The observed flame length was expressed as a function of the ratio of coaxial air to fuel jet velocity and compared with a theoretical prediction based on the velocity ratio. Four cases of fuel mixed by volume were determined: 100% H₂, 80% H₂/20% N₂, 80% H₂/20% CO₂, and 80% H₂/20% CH₄. In addition, fuel jet air velocity and coaxial air velocity were varied in an attached flame region as u_F = 86-309 m/s and u_A = 7-14 m/s. In this study, we derived a scaling correlation for predicting the flame length in a simple jet with coaxial air using the effective jet diameter in a near-field concept. The experimental results showed that the visible flame length was in good relation to the theoretical prediction. The scaling analysis is also valid for diluted hydrogen jet flames with varied fuel composition, which affects flame length by varying the density of the fuel.     

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.     

Influence of low air pressure on combustion characteristics and flame pulsation frequency of pool fires

To investigate the effect of low air pressure on the combustion characteristics and puffing flame frequency of pool fires, ethanol and n-heptane pool fires were performed using 15 square burners of various size in both Lhasa (altitude: 3650 m; air pressure: 65 kPa) and Hefei (altitude: 24 m, air pressure: 100.8 kPa) fire laboratories. Comparison of the experimental results for pool fires of the same size in the two places shows that, firstly, the maximum rise in the centerline temperature in flames in Lhasa is generally larger than that in Hefei. Secondly, the dependence of the burning rate exponent n () on the air pressure varies with the equivalent diameter D of the burner, with n < 0 (D < 7 cm), (0-1) (7 cm < D < 10 cm), (1-1.45) (10 cm < D < 19 cm) and 1 (D > 19 cm). Thirdly, radiation fraction of the pool fire flames is smaller at low air pressure. Finally, the puffing frequency of the pool fire flames is higher at low air pressure. Compared with Hefei, in Lhasa, for the same size burner, a higher maximum temperature together with less radiation from the flame is observed. This shows that in low air pressure, the pool fire is more buoyant, which leads to stronger periodic oscillation and a higher flame puffing frequency.     

Upgrading of asphalt with and without partial oxidation in supercritical water

Supercritical water and supercritical water partial oxidation treatments were applied to the upgrading of asphalt. Asphalt was converted at 613-673 K, 0-0.5 g/cm³ water density under argon or air atmosphere. Under an argon atmosphere and 0.5 g/cm³ water density, both the asphaltene conversion and desulfurization increased with increasing temperature. At 673 K, the asphaltene conversion and the yield of CO₂ increased with an increasing water density. Water apparently participated in the reaction and its hydrogen was used for capping the free radicals generated during the upgrading of asphalt resulting in an increased yield of maltene. Under an air atmosphere at 673 K, asphaltene conversion was lower but desulfurization was higher than those obtained in an argon atmosphere.     

Kinetics of biodiesel synthesis from sunflower oil over CaO heterogeneous catalyst

Calcium oxide as a heterogeneous catalyst was investigated for its effect on the biodiesel synthesis from refined sunflower oil. Experiments were carried out using a commercial bench stirred tank reactor of 2 dm³ volume, at 200 rpm, with a methanol to oil ratio 6 to 1 and 1 mas.% catalyst loading as constant parameters. Ester yields were followed as a function of temperature (60-120 °C), pressure (1-15 bars) and reaction time (1.5-5.5 h). The temperature of 100 °C was found to be optimal for the maximum (91%) conversion to methyl esters, while pressure had a positive impact up to 10 bars at 80 °C. The catalyst activation in air leading to the formation of strong basic sites was found to occur at 900 °C. Catalyst particle coalescence took place during the reaction, giving a gum-like structure, and resulted in a significant catalyst deactivation. The pseudo-first order reaction was established, with a “knee” at 80 °C in the Arrhenius plot separating the kinetic and diffusion regimes. During the reaction progress, an activation energy decrease from 161 to 101 kJ/mol, and from 32 to (−3) kJ/mol, was found for the kinetic and diffusion regimes, respectively.