Kinetics of the Absorption of Pure CO2 by Mixtures of Diisopropanolamine and Triethanolamine in Aqueous Solution

This study analyzes the absorption of pure carbon dioxide in aqueous solutions of mixtures of di‐isopropanolamine (DIPA) and triethanolamine (TEA). A stirred tank batch reactor was used with a known flat interface area. The variables considered were temperature within the range 288–313 K and concentration in the interval 5–20% (in weight), being DIPA/TEA relations 75/25, 50/50, and 25/75. The temperature control for the DIPA/TEA 75/25, 50/50, 25/75 systems in the absorption experiments, at all the concentrations and temperatures assayed, showed no differences between that of the liquid phase with respect to the operation, implying that the processes occurred under isothermal conditions. The results show that for the DIPA/TEA 75/25 CO₂ was absorbed in a moderately fast reaction regime, following a second‐order reaction for the total alkanolamine and a first‐order reaction for the CO₂, whereas for the DIPA/TEA 50/50 and 25/75 systems the process followed first‐order kinetics with respect to CO₂ and the mixture of alkanolamines, in a moderately fast reaction regime.     

Kinetics of sodium ethylenediaminetetraacetate mineralization by cerium(IV) in nitric acid medium

The process of sodium ethylenediaminetetraacetate (EDTA) mineralization by cerium(IV) in nitric acid medium was studied in batch and continuous feeding modes. In the batch mode EDTA solution was fed into the reactor in one stroke and in the continuous mode it was fed with a constant flow rate during a definite time interval. Cerium(IV) concentration was kept at high and constant level by selecting correct relation between cerium(IV) production in the electrochemical cell and the EDTA added. During the organic mineralization process cerium(IV) is reduced to cerium(III). The process was carried out at different temperatures, concentrations of nitric acid and cerium(IV). To obtain the limiting factors in the batch mode reaction, the dependence of CO₂ evolution with time and carrier gas blowing rate was studied. Application of the model previously developed by us to the continuous process gave us the possibility to calculate pseudo first order kinetic constant on the basis of CO₂ evolution data of both EDTA destruction regimes during feeding mode and after stopping organic addition. The efficiency of organic destruction estimated on the basis of CO₂ evolved was in the range 75–95% and on the basis of liquid phase residual organic carbon analysis 95–99%.     

Effects of NO2, CO,O2, and SO2 on oxidation kinetics of NO over Pt‐WO3/TiO2 catalyst for fast selective catalytic reduction process

The selective catalytic reduction rate of NO with N‐containing reducing agents can be enhanced considerably by converting a part of NO into NO₂. The enhanced reaction rate is more pronounced at lower temperatures by using an equimolar mixture of NO and NO₂. The kinetics of NO oxidation over Pt‐WO₃/TiO₂ catalyst has been determined in a fixed‐bed reactor with different concentrations of oxygen, nitric oxide, and nitrogen dioxide in the presence of 8% water. It has been found that the reaction is second order with respect to nitric oxide, first order for oxygen with a third‐order rate constant. Also, it is found that there is no effect on the reaction order with an addition of NO₂, CO, or SO₂. It follows the same second order but the reaction rate is found to be changed. It is observed that in the case of NO₂ and SO₂, the reaction rate tends to decrease, but it increases with the addition of CO into the feed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 613–620, 2006     

Kinetics of Silver-Catalysed Oxidation of dl-Atrolactic Acid (A. L. A.) by Potassium Peroxydisulphate

Kinetic data of silver catalysed oxidation of dl-atrolactic acid (A. L. A.) by peroxydisulphate ion are reported. The reaction is first order with respect to S₂O₅² ion zero order with respect to A. L. A. The rate is linearly related with Ag⁺ ion concentration. The oxidation products of A. L. A. were found to be CO₂and acetophenone, which establish the fission of C-C bond in the oxidation process. The mechanism of the reaction and inhibition by various substrats has been discussed.     

New kinetic model for the rapid step of calcium oxide carbonation by carbon dioxide

Carbonation of solid calcium oxide by gaseous carbon dioxide was monitored by thermogravimetry. A kinetic model of CaO carbonation is proposed in order to interpret the first rapid step of the reaction. By taking into account, the existence of large induction period as well as the sigmoidal shape of the kinetic curves in this kinetic-controlled region, a surface nucleation and isotropic growth kinetic model based on a single nucleus per particle is proposed, and the expressions of the fractional conversion and the reaction rate versus time are detailed. The induction period is found to have a linear variation with respect to temperature and to follow a power law with respect to CO₂ partial pressure. The areic reactivity of growth decreases with temperature increase, and increases with CO₂ partial pressure increase. A mechanism of CaCO₃ growth is proposed to account for these results and to determine a dependence of the areic reactivity of growth on the temperature and the CO₂ partial pressure.     

A simple method for analysis of consecutive reactions with a second order formation and a first order decay of an intermediate

A simple method is developed to evaluate rate constants from absorbance-time traces for a pair of consecutive reactions consisting of a second order formation and a first order decay of an intermediate. Initially, a first order profile is simulated utilizing the data near the end of the reaction. The difference between this simulated and observed profiles provides the absorbance-time data for the initial phase from which a second order rate constant is evaluated. These rate constants were used to simulate composite kinetic curves which were then compared with experimental curves. This method was used to test the reaction between cis-Pt(NH₃)₂(H₂O)₂ ²⁺ and a nonapeptide, ERFKCPCPT. The reaction proceeds through a cysteine coordinated intermediate formed in a second order process (first order with respect to each reactant). The intermediate is then converted to a product through a first order process, in which both cysteines are coordinated to platinum(II).     

Decomposition of Toluene and Acetone in Packed Dielectric Barrier Discharge Reactors

The influences of TiO₂ catalytic material and glass pellet packing on the decomposition efficiency of toluene and acetone in air by dielectric barrier discharge (DBD) reactors were experimentally investigated in this study. The effects of both packing materials on the formation of byproducts such as CO and CO₂ were also evaluated. Experimental results indicate that the introduction of glass materials into the plasma zone of a wire-tube reactor would improve the decomposition efficiency of toluene and acetone compared to a nonpacked reactor. The apparent decomposition rate constant of a glass packed-bed reactor was 4.5–4.8 times greater than that of a nonpacked reactor. The results also indicate that the decomposition rate constant of toluene was approximately 2.6 times higher than that of acetone no matter which type reactor was utilized. The application of TiO₂ coated pellets in DBD reactors will enforce the hydrocarbon byproducts to further be oxidized to CO₂, notwithstanding, it will not significantly improve the performance of the reactors in the decomposition of toluene and acetone, and in the formation of CO. The results show that the best selectivity of CO₂ for acetone decomposition in a TiO₂ coated pellets packed-bed reactor was approximately 40% higher than that in a glass packed-bed reactor.     

Effect of metal oxides on the reforming of methane with carbon dioxide

The effect of basic and rare earth metal oxides on the stability of nickel-based catalysts for the CO₂ reforming of CH₄ has been studied. The addition of metal oxides increased the stability of Ni-based catalysts and reversed the values of the reaction orders with respect to both CH₄ and CO₂. In the presence of metal oxides, the values of the reaction orders with respect to CO₂ partial pressure followed the same trend of catalyst stability.     

Kinetics of isobutylene oxidation on a Mo-Sb-Te-O (1 : 0.6 : 0.06) catalyst

Kinetics of isobutylene oxidation over a Mo-Sb-Te-O catalyst is studied in a flow-circulation system with the Korneichuk differential reactor. The reaction orders of methacrolein, acetic acid, acetone, and CO₂ formation, as well as the order of the overall reaction of isobutylene oxidation into methacrolein, with respect to oxygen and isobutylene are determined at 613–703 K and oxygen concentrations of (0.33–13.05) x 10⁻³ mol/1 and isobutylene (3.2–121.9) × 10⁻⁴ mol/1. The activation energies of these reactions are determined.     

Photooxidation of carbonyl sulfide in the presence of the typical oxides in atmospheric aerosol

Carbonyl sulfide (COS) is one of the most abun-dant sulfur containing gases in the troposphere andlower stratosphere[1,2]. It is relatively inert in the tro-posphere and can be transported into the stratosphere,where it dissociates under the solar ultravi…     

H + HOONO2 → products: Temperature-dependent rate constant

The absolute reaction rate constant of the title reaction was measured in a stirred-flow reactor under H-atom-rich conditions at seven temperatures from 226 to 315 K. Carbon monoxide was added to convert any OH radicals produced back to H atom by way of the reaction OH + CO → H + CO₂. The reaction rate constants were essentially constant between 248 and 315 K: (k ± 2σ) = (2.46 ± 0.35) × 10^?14 cm³/s. At temperatures lower than 248 K, the measured rate constant became larger at lower temperatures, possibly due to heterogeneous effects. An hypothesis is advanced that may explain the surprisingly slow rate constant that is virtually independent of temperature, but more experiments are required to determine the dynamical reaction pathway.     

A new reforming process based on CH4 decomposition using a hydrogen-permeating membrane reactor

A new reforming process was studied using Ni/SiO₂ with a hydrogen-permeating membrane reactor. Nickel catalyst supported on SiO₂ is highly active for CH₄-H₂O-O₂ reaction in membrane reactor and the reaction close to CH₄ + 0.35O₂ + 1.3H₂O → CO₂ + 3.3H₂ proceeds at 873 K. Since the selectivity to carbon and CO₂ increased and decreased with decreasing contact time respectively, it is considered that the reaction was started by decomposition of CH₄ followed by oxidation of C and water shift reaction. Therefore, the reaction mechanism was different from so-called autothermal reforming (ATR) reaction.     

Mechanism and Kinetics of Carbon Dioxide Capture Using Activated 2‐Amino‐2‐methyl‐1,3‐propanediol

The continued use of fossil fuels as primary sources of energy in industry and other applications stands the test of time, due to their availability and relatively lower cost than alternative sources of energy. In view of this perspective, obtaining an advanced bulk carbon dioxide (CO₂) capture medium becomes an urgent necessity so as to mitigate their effect, especially in global warming, as the use of fossil fuels produces a high rate of CO₂. In this work, the mechanism and kinetics of CO₂ capture using aqueous piperazine (PZ) as an activator to 2‐amino‐2‐methyl‐1,3‐propanediol (AMPD) were investigated. The termolecular mechanism was used to model the kinetics of the system. Reaction kinetics of the single pure amines was first obtained. The reaction rate constant, the k value of AMPD, was 77.2 m³/kmol·s, with a reaction order, n, of 1.25 at 298 K. while that of PZ was equal to 11,059 m³/kmol·s and n as 1.49 at 298 K. Blending of 0.05 kmol/m³ of PZ with 0.5 kmol/m³ of AMPD gave a rate constant, k, value of 23,319 m³/kmol·s and n equal to 1.23 at 298 K. The result obtained for the blended system is more than twice the value of the summation of the corresponding pure amines; in addition, it is comparably higher than the rate constant of monoethanolamine (MEA) in use as a commercial solvent for CO₂ capture. Therefore, an aqueous blend of PZ with AMPD deserves more comprehensive study as a solvent for commercial CO₂ capture. AMPD like other sterically hindered amines absorbs CO₂ in an equimolar ratio that is significantly higher than that of MEA. PZ serves as a promoter in the amine mixture and is required in a very small proportion.     

A new reforming process based on CH4 decomposition using a hydrogen-permeating membrane reactor

A new reforming process was studied using Ni/SiO₂ with a hydrogen-permeating membrane reactor. Nickel catalyst supported on SiO₂ is highly active for CH₄?H₂O?O₂ reaction in membrane reactor and the reaction close to CH₄+0.35O₂+1.3H₂O→CO₂+3.3H₂ proceeds at 873 K. Since the selectivity to carbon and CO₂ increased and decreased with decreasing contact time respectively, it is considered that the reaction was started by decomposition of CH₄ followed by oxidation of C and water shift reaction. Therefore, the reaction mechanism was different from so-called autothermal reforming (ATR) reaction.     

Kinetics of carbon dioxide sorption by the composite material K2CO3 in Al2O3

The kinetics of the CO₂ sorption by a composite sorbent K₂CO₃ in Al₂O₃ was studied in a gradientless adsorber at 295 K. The order of the sorption rate with respect to the CO₂ concentration was found to be n = 1.04 ± 0.07. The sorption rate constants were evaluated for sorbent grains of various sizes between 0.25 and 2.1 mm. It was shown that the rate constant is proportional to the grain reciprocal radius. The dynamic capacity was obtained as a function of the CO₂ concentration. The maximum sorption capacity was found to be 83 mg of CO₂ per 1 g of the sorbent. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Microwave-Assisted Boudouard Reaction: A Highly Effective Reduction of the Greenhouse Gas CO2 to Useful CO Feedstock with Semi-Coke

The conversion of CO₂ into more synthetically flexible CO is an effective and potential method for CO₂ remediation, utilization and carbon emission reduction. In this paper, the reaction of carbon-carbon dioxide (the Boudouard reaction) was performed in a microwave fixed bed reactor using semi-coke (SC) as both the microwave absorber and reactant and was systematically compared with that heated in a conventional thermal field. The effects of the heating source, SC particle size, CO₂ flow rate and additives on CO₂ conversion and CO output were investigated. By microwave heating (MWH), CO₂ conversion reached more than 99% while by conventional heating (CH), the maximum conversion of CO₂ was approximately 29% at 900 °C. Meanwhile, for the reaction with 5 wt% barium carbonate added as a promoter, the reaction temperature was significantly reduced to 750 °C with an almost quantitative conversion of CO₂. Further kinetic calculations showed that the apparent activation energy of the reaction under microwave heating was 46.3 kJ/mol, which was only one-third of that observed under conventional heating. The microwave-assisted Boudouard reaction with catalytic barium carbonate is a promising method for carbon dioxide utilization.     

Kinetics of oxidative degradation of pantothenic acid by cerium(IV) in aqueous perchloric acid

The kinetics of oxidation of pantothenic acid (PA), Me₂C(CH₂OH)CH(OH)C(O)NHCH₂CH₂CO₂H, by cerium(IV) in aqueous HClO₄ medium at constant ionic strength, 2.0 mol dm^–3, has been studied spectrophotometrically. The reaction showed first-order kinetics in Ce^IV concentration, an apparent less than unit order dependence in [PA] and an inverse fractional order in [H⁺]. Initial addition of products had no significant effect on the rate of the reaction. A possible mechanism is proposed, and the reaction constants involved in the mechanism have been computed. There is good agreement between the observed and calculated rate constants under different experimental conditions. The activation parameters were calculated with respect to the slow step of the proposed mechanism.     

Time-Resolved CO<Subscript>2</Subscript> Dissociation in a Nanosecond Pulsed Discharge

Electrical discharges are increasingly used to dissociate CO₂ in CO and O₂. This reaction is the first step in the way for the synthesis of value-added compounds from CO₂ by using renewable electricity. If efficient, this technology might allow at the same time recycling CO₂ and storing renewable energy in chemical form. At present, while the dissociation degree is measured in the reactor exhaust, little is experimentally known about the dissociation kinetics in the discharge and post-discharge. This knowledge is however critical to increasing the overall efficiency of the plasma process. To estimate the time dependence of the CO₂ dissociation following a discharge event, we have coupled a LIF diagnostics to a nanosecond repetitively pulsed discharge in a mixture of CO₂ and H₂O. This paper discusses a procedure to obtain data on the time evolution of the CO₂ dissociation, its limits and future perspectives. In addition, the local gas temperature is measured as well. We find that a few microseconds after the discharge pulse, CO₂ is highly dissociated with a temperature around 2500 K. In about 100 µs, the temperature decreases at about 1500 K while the dissociation is reduced by about a factor of three.     

Application of non-thermal atmospheric pressure ac plasmas to the carbon dioxide reforming of methane

Methane conversions of 11.9%, yields of hydrogen as high as 23.3% and energy yields of 1.0 mol H₂/kWh have been achieved from CO₂ reforming of CH₄ in non-thermal, atmospheric pressure plasma reactors with Pt coated electrodes. Two reactors have been studied. A novel fan type reactor consisting of a movable rotor and immobile stator produced the highest yields in contrast to a tube type (silent discharge) reactor with a glass dielectric barrier. Conversions, yields of hydrogen and energy yields (expressed as mol H₂/kWh) were studied for CO₂/CH₄ concentrations of 1.1% and 5.0% in He as a function of flow rate and input voltage. Hydrogen yields are observed to increase as the input voltage is increased from 411 V to 911 V and the flow rate is decreased from 100 cc/min to 30 cc/min. Energy yields vary only slightly with input voltage and flow rate. Hydrogen yields show little dependence on CO₂/CH₄ concentrations, but energy yields are approximately five times greater for the 5.0% mixture than the 1.1% mixture. Selectivities to H₂, CO, coke, and low molecular weight hydrocarbons were also evaluated and compared to data obtained without CO₂ in the feed. Hydrogen selectivities of nearly 100% were obtained, with small amounts of ethane and propane as the only observed side products and the selectivites were approximately the same whether CO₂ was present or absent in the mixture. However, the reaction proceeds much more cleanly when CO₂ is present, producing CO. The syngas product has an H₂ : CO ratio of 1.5 with the fan type reactor and 0.67 with the tubular reactor. In the absence of CO₂, coke is the main carbonaceous product. Under all conditions studied the fan type reactor demonstrated higher methane conversions (up to 11.9%) and selectivities to hydrogen.     

Oxidation of aspartic acid by Cu(III) complex in alkaline medium: A kinetic and mechanistic study

The kinetics and mechanism of oxidation of aspartic acid by the bis(hydrogen periodato) complex of Cu(III), [Cu(HIO₆)₂]^5?, is studied in an alkaline medium. The reaction rate is first order with respect to Cu(III) and fractional order with respect to aspartic acid. The value of the observed rate constant is found to decrease with the increase in concentrations of either OH^? or IO₄ ^?. There is a positive salt effect, and the free radical has been determined. In view of these kinetics phenomena, a plausible mechanism is proposed and the rate equations derived from the mechanism can explain all experimental results. The activation parameters along with the rate constants of the rate-determining step are calculated.