Kinetics of redox reactions of ilmenite for chemical-looping combustion

The objective of this study was to establish the kinetic of both reduction and oxidation reactions taking place in the chemical-looping combustion (CLC) process using ilmenite as an oxygen carrier. Because of the benefits of using of pre-oxidized ilmenite and the activation of the ilmenite during the redox cycles, the reactivity of both the pre-oxidized and activated ilmenite was analyzed. The experimental tests were carried out in a thermogravimetric analyzer (TGA), using H₂, CO or CH₄ as reducing gases, and O₂ for the oxidation step. Thus, the reactivity with the main reacting gases was analyzed when natural gas, syngas or coal are used as fuels in a CLC system. The changing grain size model (CGSM) was used to predict the evolution with time of the solid conversion and to determine the kinetic parameters. In most cases, the reaction was controlled by chemical reaction in the grain boundary. In addition, to predict the behaviour of the oxidation during the first redox cycle of pre-oxidized ilmenite, a mixed resistance between chemical reaction and diffusion in the solid product was needed. The kinetic parameters of both reduction and oxidation reactions of the pre-oxidized and activated ilmenite were established. The reaction order for the main part of the reduction reactions of pre-oxidized and activated ilmenite with H₂, CO, CH₄ and O₂ was n=1, being different (n=0.8) for the reaction of activated ilmenite with CO. Activation energies from 109 to 165 kJ mol⁻¹ for pre-oxidized ilmenite and from 65 to 135 kJ mol⁻¹ for activated ilmenite were found for the different reactions with H₂, CO and CH₄. For the oxidation reaction activation energies found were lower, 11 kJ mol⁻¹ for pre-oxidized and 25 kJ mol⁻¹ for activated ilmenite.Finally, simplified models of the fuel and air reactors were used to do an assessment of the use of ilmenite as an oxygen carrier in a CLC system. The reactor models use the reaction model in the particle and the kinetic parameters obtained in this work. Taking into account for its oxygen transport capacity, the moderated solids inventory and the low cost of the material, ilmenite presents a competitive performance against synthetic oxygen carriers when coal or syngas are used as fuel.     

Understanding chemical reactions between carbons and NaOH and KOH: An insight into the chemical activation mechanism

Direct mixing of an anthracite with hydroxides (KOH or NaOH) and heat treatment up to 730 °C has shown to be a very good activation procedure to obtain activated carbons with very high surface areas and high micropore volumes. The reactions involved during the heat treatment of these hydroxide/anthracite mixtures have been analysed to deep into the fundamental of the knowledge of this chemical activation process, that has not been studied before. For this purpose, the present paper analyses the drying process, the atmosphere during the carbonisation, the chemical state of the activating agents (NaOH, KOH and Na₂CO₃) and the chemical reactions occurring during the heat treatment which have been followed by FTIR and TPD. The analysis of our results allows us to conclude that steam is a good atmosphere for the carbonisation process, alone or joined with nitrogen, but not as good as pure nitrogen. On the other hand, during the activation process, the presence of CO₂ should be avoided because it does not develop porosity. The reactions, and chemical changes, involved during this chemical process are discussed both from a thermodynamical point of view as well as identifying the reaction products (H₂ by TPD and Na₂CO₃ by FTIR). As a result, this paper helps to cover the present lack of understanding of the fundamentals of the reactions of an anthracite with hydroxides which are necessary to understand the activation of the material.     

Effects of chemical modification of petroleum cokes on the properties of the resulting activated carbon

Activated carbons have been prepared from petroleum cokes by the combination of a chemical treatment with HClO₄ or H₂O₂ and a chemical activation with KOH at a constant KOH/coke ratio of 3/1. The influence of different chemical treatments on the properties of the activated carbon precursors and final carbons activated with KOH was invested by using XRD, FTIR, and BET techniques. XRD results indicated that the value of interplanar distance d₀₀₂ increased by chemical treatment and the disappearance of the peak corresponding to 0 0 2 faces correlated to high specific surface area. FTIR studies showed that chemical modification promoted the formation of surface oxygen functionalities. Significant effects on BET surface area, pore texture and iodine adsorption capacity were evidenced. The results show that chemical modification prior to activation dramatically increased the BET surface area and total pore volume of the resulting activated carbon. Modified petroleum coke based activated carbon with chemical activation had higher specific surface area (2336 m²/g) and better iodine adsorption value (1998 mg/g).     

NMR investigation on the occurrence of Na species in porous carbons prepared by NaOH activation

A detailed investigation was conducted about the process of alkali activation of charred rice hulls using NaOH. A carbon-rich precursor was initially prepared from the pyrolysis of rice hulls under N₂ atmosphere, part of it being leached with HF to remove silica. The precursor was then mixed with NaOH, heat-treated at activation temperatures from 600 to 800 °C, and part of the product was finally washed with distilled water. Thermogravimetric curves under O₂ flux showed a strong reduction in the ash content of the activated samples, indicating the consumption of silica during the activation process. From X-ray diffractometry, ²⁹Si, and ²³Na NMR spectroscopy, it was possible to identify the formation of sodium carbonate and silicates in the non-washed samples. After washing, all these compounds were removed and specific surface area measurements indicated a substantial porosity development, with larger surface area values obtained for the samples prepared from the HF-leached precursor. The use of ²³Na NMR spectroscopy indicated the retention of sodium in the washed samples, in a chemical environment distinct from carbonates and silicates. The shapes and positions of the observed resonance lines pointed to a disordered environment, associated with oxygenated surface groups within the porous structure of the activated carbons.     

Effect of Gasifying Medium on the Coal Chemical Looping Gasification with CaSO4 as Oxygen Carrier

The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with CaSO₄ as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO₂ into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value. Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium (steam or CO₂) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO₂. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO₂ as the gasifying medium.     

Comparative study of the textural characteristics of oil palm shell activated carbon produced by chemical and physical activation for methane adsorption

The objective of this study is to relate textural and surface characteristics of microporous activated carbon to their methane adsorption capacity. Oil palm shell was used as a raw material for the preparation of pore size controlled activated carbon adsorbents. The chemical treatment was followed by further physical activation with CO₂. Samples were treated with CO₂ flow at 850 °C by varying activation time to achieve different burn-off activated carbon. H₃PO₄ chemically activated samples under CO₂ blanket showed higher activation rates, surface area and micropore volume compared to other activation methods, though this sample did not present high methane adsorption. Moreover, it was shown that using small proportion of ZnCl₂ and H₃PO₄ creates an initial narrow microporosity. Further physical activation grantees better development of pore structure. In terms of pore size distribution the combined preparation method resulted in a better and more homogenous pore size distribution than the conventional physical activation method. Controlling the pore size of activated carbon by this combined activation technique can be utilized for tuning the pore size distribution. It was concluded that the high surface area and micropore volume of activated carbons do not unequivocally determine methane capacities.     

Acquiring real kinetics of reactions in the inhibitory atmosphere containing product gases using micro fluidized bed

This study proposed an isotope-tagging method to investigate reactions under the atmosphere of product gas. To illustrate this method, the calcination kinetics of calcium carbonate Ca¹³CO₃ in CO₂ atmospheres were investigated by monitoring ¹³CO₂ produced using a micro fluidized bed reaction analyzer (MFBRA). The results demonstrated that the presence of CO₂ in reaction atmosphere increases the apparent activation energy. The increase in the apparent activation energy is, however, significantly overestimated by the thermogravimetric analyzer (TGA) because of the excessive suppression by stagnated product gas inside the sample crucible. Comparatively, the apparent activation energy increases with CO₂ from the MFBRA due primarily to the thermal equilibrium limitation, because the gas diffusion in the MFBRA is essentially eliminated. It is thus concluded that the MFBRA is quite capable of acquiring the real kinetics of reactions in such inhibitory atmospheres.     

Treating contaminated soil by conversion into carbonaceous adsorbents: an investigation of activation procedures

The well established activated carbon manufacturing process has been investigated as a novel treatment for contaminated soil from gaswork sites by converting it into a porous carbonaceous solid with adsorbent properties. Several activation methodologies were evaluated: CO₂, air, ZnCl₂, H₂SO₄, H₃PO₄, FeSO₄ and HNO₃. Thermal analysis of the soil provided information regarding appropriate carbonisation and activation conditions. Bulk samples were prepared using contaminated soil samples, with ZnCl₂ being found to be the most effective agent for the process, producing an adsorbent which possessed a BET surface area of 131m²g⁻¹. The aqueous adsorption ability of the soil carbons was studied using phenol and 4‐nitrophenol as representative micropollutant organic molecules. The Langmuir monolayer capacity of the ZnCl₂‐activated soil was found to be 0.12 mmg⁻¹ for phenol and 0.23 mmg⁻¹ for 4‐nitrophenol. © 2000 Society of Chemical Industry     

Reactions with Aziridines,XXXII[1]. Mechanistic Aspects in Nucleophilic Opening of Three-Membered Rings. Alcoholyses of Activated Aziridines

Nucleophilic ring opening of three-membered rings is discussed in terms of leaving group basicity. Reactions of activated (weakly basic leaving groups) 2,2-dimethylaziridines 5 and 2-phenylaziridines 6 with alcohols ROH are studied with reference to the site selectivity of ring opening and competing side-reactions. Abnormal opening (at the substituted carbon) of 5 proceeds in neutral ROH without catalyst when the activation is strong (tosyl) whilst no reaction or mainly carbonyl attack is observed with weak activation (CONHAr). NaClO₄ catalyzes the abnormal opening of 5. EtO⁻ gives exclusively normal opening of 5 whilst, in contrast to the literature, MeO⁻ gives also a substantial amount of abnormal ether. Attack on 6 always occurs at both positions with the predominance of the abnormal reaction being greater for MeO⁻ than for EtO⁻. These reactions are considered S_N2 with steric and benzylic differentiation between normal and abnormal attack depending on the size of ROH. Acid catalyzed openings of 5 and 6 proceed exclusively abnormally in the ether-forming reaction as well as in side-reactions. Competition experiments and increase of the side-reactions with the size of ROH demonstrate a deceleration of the ether-forming reaction with the size of ROH. Obviously, the side-reactions originate from a carbenium ion whilst the ethers are mainly formed by a borderline mechanism. R(-)6b and acidic MeOH give only 8% racemization in the abnormal ether. An order of activation is proposed for activated aziridines under acid catalysis (double activation).     

Al2O3·2SiO2 powders synthesized via sol–gel as pure raw material in geopolymer preparation

Geopolymers are inorganic aluminosilicates mainly proposed as environmentally friendly building materials, which are obtained by alkali activation of natural minerals, calcined clay (e.g., metakaolin) and other aluminosilicate sources. The wide range of chemical and mineralogical compositions of these raw materials influences several properties of the obtained geopolymers. In the present work, pure Al₂O₃·2SiO₂ powders were synthesized via the sol–gel technique and proposed as pure aluminosilicate sources to prepare alkali activated geopolymers. Samples differing in the ratio between the SiO₂ precursor and the H₂O used in the sol–gel process were prepared, in order to study the effect of water content on the material structure and reactivity. The chemical structure of all the obtained Al₂O₃·2SiO₂ powders were characterized by Fourier transform infrared (FT‐IR) and solid‐state nuclear magnetic resonance (²⁷Al and ²⁹Si MAS NMR) spectroscopies and compared to that of a reference metakaolin. Moreover, material reactivity was evaluated by alkali activation of the samples. After 28 days of ageing, ²⁷Al and ²⁹Si MAS NMR and FT‐IR spectra ascertained the formation of a geopolymeric network in the activated samples. The results showed that lower water content allows obtaining a homogeneous Al‐rich geopolymer similar to that obtained, using metakaolin as raw material.     

Reaction kinetics to infer the effect of dopants on ion transport - A case study for Mo+6 doped lithium titanates (Li2TiO3-δ and Li4Ti5O12-δ)

In this paper, a unique approach to correlate influence of doping on ionic mobility, through thermo-kinetic analysis, is reported. Formation kinetics of Li₂TiO₃ and Li₄Ti₅O₁₂, with Mo⁺⁶ doping, were successfully analyzed in ultra-pure Ar atmosphere using differential scanning calorimetry. The results were compared with formation kinetics of pure Li₂TiO₃ and Li₄Ti₅O₁₂ under identical conditions. Field emission scanning electron microscopy (FE-SEM) with electron diffraction spectroscopy (EDS), X-ray diffraction and Raman spectroscopy were employed for the characterization of resulting phases and presence of oxygen vacancy. The results indicate that for doped samples, oxygen vacancy concentration was reduced due to the charge compensation mechanism of the doped ion. The activation energy (E_α) of the different reactions with and without Mo⁺⁶ doping was determined by Kissinger-Akahira-Sunose method. The most probable reaction mechanism was predicted through Master plot approach. The reaction rate controlling step shifted from three-dimensional diffusion (D₃) for undoped Li₂TiO₃ to a chemical reaction (F_n) for doped Li₂TiO₃. For Li₄Ti₅O₁₂ the reaction mechanism (or rate controlling step) was a chemical reaction (F_n) for undoped and nucleation (A_n) for doped material. The results show that diffusion of ions becomes faster in the Mo⁺⁶ doped materials by reducing the charge transfer resistance. Finally, the thermodynamic functions of the transition complex were calculated from kinetic triplets and correlated with thermo-kinetic data.     

Activation of coal tar pitch carbon fibres: Physical activation vs. chemical activation

Activated carbon fibres (ACF) are obtained mainly by physical activation with steam or carbon dioxide. Additionally, there are many papers dealing with chemical activation of carbon fibres, or a polymeric raw material, with several chemical agents like for example, phosphoric acid, zinc chloride, aluminium chloride,… Nevertheless, although it is well known that hydroxides are good activating agents, there are few papers about the activation of carbon fibres with KOH or NaOH. In the present work, ACF with high surface area are obtained by chemical activation with KOH and NaOH. Both chemical agents present different behaviour; thus, NaOH developed the highest value of porosity and KOH developed samples with narrower micropore size distribution. In order to compare the results with those obtained by physical activation, some ACF have been prepared using CO₂ activation. The main conclusion of this work is that by using chemical activation it is possible to obtain similar, or even higher, porosity (∼1 ml/g, ∼3000 m²/g) than by physical activation. However, chemical activation presents two important advantages: (1) a much higher yield (27-47% for chemical activation and 6% physical activation for ∼2500 m²/g activated carbon fibres) and (2) the surface of the fibres prepared by chemical activation is less damaged than by physical activation.     

A comparison of physical activation of carbon xerogels with carbon dioxide with chemical activation using hydroxides

Carbon xerogels synthesized with a fixed resorcinol/sodium carbonate molar ratio (R/C) were physically activated using CO₂. The effect of activation temperature and activation time on the final properties of the activated carbon xerogels was evaluated. The specific surface area increases from ∼600 m² g⁻¹ to 2000 m² g⁻¹ and more by increasing the temperature and duration of the activation step. A comparison between physical activation with CO₂ and chemical activation with hydroxides was also performed: it was found that both processes produce an increase of the micropore volume and specific surface area without altering the mesoporosity developed during the synthesis. However, chemical activation can lead to the development of the narrow microporosity mainly whereas, in physical activation, the widening of the narrow micropores takes place whatever the process conditions.     

The factors affecting the performance of activated carbon prepared from oil palm empty fruit bunches for adsorption of phenol

Powdered activated carbons (PACs) were produced from oil palm empty fruit bunches (EFB) by varying the operating parameters of temperatures, CO₂ gas flow rates and activation times using 2-level full factorial experimental design. The EFB samples were first carbonized for 30 min using nitrogen gas followed by physical activation using CO₂ to optimize best production conditions. The optimum conditions for PACs produced were investigated through adsorption tests on aqueous solution of phenol. The results of this study demonstrated that the activation temperature with the range of 800–900 °C had the most significant effect on the adsorption characteristics as well as the yield of the activated carbon produced. Based on the analysis of variance (ANOVA) and model equation developed, the optimum production conditions for the EFB PAC were found to be at the activation temperature of 900 °C with CO₂ gas flow rate of 0.1 L/min and activation time of 15 min. Characterization of PAC produced showed that the activation conditions would find good-quality adsorbent with the BTE surface area of 345.1 m²/g and well forming pores distribution.     

Effect of Thermal Activation on the Kinetics of Cd2+ Ions Sorption by AlPO4

Abstract

The kinetics of Cd²⁺ uptake on two different samples of AlPO₄ activated at 105°C and 400°C is studied as a function temperature, which shows an increase in the optimum time for the maximum uptake of Cd²⁺ ions with activation. The mechanism of the uptake is observed to change from ion exchange to sorption inside the pores with activation. The rate constants calculated from the first order Lagergren's plots are observed to decrease while activation energy, enthalpy, entropy, and free energy of activation are observed to increase with activation. All the activation parameters are found to be higher for the activated AlPO₄ as compared to the non-activated AlPO₄.     

Activation of olive-seed waste residue using CO2 in a fluidized-bed reactor

Physical activation of olive-seed waste residue was carried out under N₂/CO₂ atmosphere in a fluidized-bed reactor system. The effects of activation temperature, activation time and particle size on both yield and quality of the prepared products were studied. The quality was measured in terms of iodine number and adsorptive capacity towards methylene blue dye. In general, it was found that higher activation temperature, longer activation time and smaller particle size produced a higher quality activated carbon. The products were compared to a commercial grade activated carbon prepared by steam activation process. Samples of 0.71–0.85 mm particle size activated at 900°C and activation time greater than 60 min were superior to the commercial carbon. Similar results were obtained for similar samples activated at 800°C and activation times greater than 60 min. A kinetic model was applied to the data. A first order reaction kinetics was found to fit the experimental data well. The value of the rate constant for activation was found to be 0.65 s⁻¹.     

Preparation and characterization of activated carbons for SO<Subscript>2</Subscript> adsorption from Taixi anthracite by physical activation with steam

Taixi anthracite was used as a precursor to prepare activated carbons (AC) for SO₂ adsorption from flue gas. In this work the activated carbons were prepared by physical activation with steam. Specifically, the effects of activation temperature and burn-off degree on the physico-chemical properties of the resulting AC samples were comparatively studied. The different types of pore volumes, pore size distributions and surface chemistries of the activated carbons on the SO₂ adsorption were also analyzed. The results show that the increasing burn-off leads to samples with continuous evolution of all types of pores except ultramicropore. The ultramicropore volume increases to a maximum of 0.169 cm³/g at around 50% burn-off and then decreases for 850 °C activation. At higher activation temperature, the micropore volume decreases and the mesopore structure develops to a certain extent. For all the resulting AC samples, the quantities of the basic surface sites always appear much higher than the amount of the acidic sites. The activated carbon prepared with higher micropore volume, smaller median pore diameter and higher quantities of the basic surface sites represents better SO₂ sorption property.     

Effect of activation on the carbon fibers from phenol–formaldehyde resins for electrochemical supercapacitors

Activated carbon fibers (ACF) are prepared from phenol–formaldehyde resin fibers through chemical activation and physical activation methods. The chemical activation process consisted of KOH, whereas the physical activation was performed by activation in CO₂. The characteristics of the electrochemical supercapacitors with carbon fibers without activation (CF), carbon fibers activated by CO₂ (ACF-CO₂), and carbon fibers activated by KOH (ACF-KOH) have been compared. The activated carbon fibers from phenol–formaldehyde resins present a broader potential range in aqueous electrolytes than activated carbon and other carbon fibers. Activation does not produce any important change in the shape of starting fibers. However, activation leads to surface roughness and larger surface areas as well as an adapted pore size distribution. The higher surface areas of fibers treated by KOH exhibited higher specific capacitances (214 and 116 F g⁻¹ in aqueous and organic electrolytes, respectively) and good rate capability. Results of this study suggest that the activated carbon fiber prepared by chemical activation is a suitable electrode material for high performance electrochemical supercapacitors.     

Radial distribution of porosity in spherical activated carbon particles

The radial distribution of porosity in spherical activated carbon particles and its relationship to both activation temperature and conversion of the reaction C-CO₂ are discussed. Char spheres, obtained by pelletizing Quercus agrifolia powdered char, were activated using CO₂ as activating agent at 820 and 860 °C. For both temperatures, the gasification reaction was run until the desired conversion (30, 50 and 70%) was reached. The activation process was performed using TGA apparatus. The porosity of the samples was measured by physical adsorption of nitrogen at −196 °C. BET and Dubinin-Raduskhevich equations were used to analyse the results. From each activated carbon sphere several samples were prepared, corresponding to different layers of the sphere; an outer layer, a middle layer and the core of the particle. From these results, the radial porosity evolution as a function of activation temperature and reaction conversion was obtained and a mathematical expression that correlates pore volume evolution and reaction conversion is proposed.     

The formation of feldspar strontian (SrAl2Si2O8) via ceramic route: Reaction mechanism,kinetics and thermodynamics of the process

The reaction mechanism, the equilibrium composition, the temperature range of stability of formed intermediates as well as the kinetics and thermodynamics of activated state during the formation of monoclinic strontium-aluminum-silicate feldspar stroncian (SrAl₂Si₂O₈) via the ceramic route from the mixture of SrCO₃, Al₂O₃ and SiO₂ is described in this work. Strontian does not appear up to the temperature of 1150 °C and is the only stable phase at the temperature ≥1600 °C. Three independent reactions lead to two parallel reaction pathways, i.e. the formation of strontian from single or binary oxides (1) and with Sr-gehlenite as the intermediate (2). Since the reaction rate constants ratio is higher than one (k₁/k₂>1), the first reaction route is favored according to the Wegscheider principle. The kinetics of chemical reaction of 1.5 order corresponding to the kinetic function F_2/3 ((1−α)^−1/2−1) was determined as the rate determining the mechanism of formation of strontian. The integral and differential methods show that the process requires average apparent activation energy of 229.3 kJ mol⁻¹. The determined average value of frequency factor is 2.1×10⁵ s⁻¹.