Study of the dichromate-catalysed hydrogen peroxide decomposition: Comparison of different batch mode reactors for the kinetics determination

Frikha, Nader; Schaer, Éric; Houzelot, Jean-Léon

doi:10.1016/j.tca.2005.06.017

Cited by 6 publications

(6 citation statements)

References 8 publications

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“…The other is an iron-catalyzed reaction; thus, the hydrogen peroxide rate equation has two sets of terms. These rate equations were assumed to have an Arrhenius form with activation energy values taken from the literature. , The heat of decomposition was also set at a literature value. , While the heat of dilution and heat of mixing of these solutions resulted in an increase in temperature, often amounting to 10–15 ° C, they are not considered in the rate equations. The starting point for the reaction is assumed to be the temperature to which the solution arrives after mixing.…”

Section: Methodsmentioning

confidence: 99%

Predicting the Autoaccelerating Hydrogen Peroxide Decomposition Rate after Mixing with Sodium Hydroxide

Houtman

Hart

2022

Ind. Eng. Chem. Res.

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Due to the large amount of inherent chemical energy, implementation of hydrogen peroxide pulp bleaching requires a high level of safety design and process review. Even with safety controls, in-place accidents have occurred at kraft pulp bleaching facilities. Using a combination of experiments and chemical engineering analysis, we present a validated model of hydrogen peroxide decomposition under alkaline conditions that are typically found in kraft pulp bleaching processes. Using the model, we then calculated several characteristic parameters required to determine the criticality class and control system safety integrity level (SIL) for an industrial-scale bleaching process. When designed for 10 wt % hydrogen peroxide, pulp bleaching systems are inherently safe as long as it is used in a process with adequately sized pressure relief. Process designs using greater than 10 wt % hydrogen peroxide require controls with SIL 4, which is the highest level of control. This level is required for processes that present the most risk and have the most severe consequences. Regardless of the hydrogen peroxide concentration, processes without adequately sized pressure relief should never be considered safe. Finally, both the experimental and model results show the dramatic acceleration of hydrogen peroxide decomposition by iron. Because membrane-grade sodium hydroxide often has an order of magnitude lower concentration of iron than diaphragm-grade sodium hydroxide, choosing membrane-grade results in reduction in potential hazard.

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Section: Methodsmentioning

confidence: 99%

Predicting the Autoaccelerating Hydrogen Peroxide Decomposition Rate after Mixing with Sodium Hydroxide

Houtman

Hart

2022

Ind. Eng. Chem. Res.

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“…A preliminary kinetic study (Frikha et al, 2005) allowed determining the kinetic and thermodynamic parameters of this reaction: Experimental implementation: In each vessel of the DCS, a predetermined quantity of hydrogen peroxide solution is loaded, while the catalyst is added in only one of the vessel and is, before the reaction begins, separated of the reactional medium by a small membrane. It is important to introduce in each vessel a same quantity of reactional media in order to respect the symmetry of the heat capacities of the measuring devices.…”

Section: Application To the Measurement Of Reaction Kineticsmentioning

confidence: 99%

“…In order to check the relevance of this methodology to evaluate reaction kinetics, we did not directly try to identify the parameters of kinetic law using the temperature profiles. Indeed, we have already described in a former paper (Frikha et al, 2005) an installation made up of two laboratory scale reactors (heat jacketed reactors of a few hundred milliliters) which are placed in parallel to operate in a similar way to the vessels of a DSC: One in which the reaction is carried out, the other one being used as reference. The advantage of such a configuration is that the temperature can easily be measured inside and outside (in the jacket) each reactor.…”

Section: Heat and Mass Balancesmentioning

confidence: 99%

“…When implementing under identical experimental conditions, i.e., with a linear variation of the external temperature, the dichromate catalysed hydrogen peroxide decomposition in such a device, we have been able to recompute, using a differential thermal analysis approach, the kinetics of the reaction with a very good accuracy. We do not develop here the analysis presented in the preceding article (Frikha et al, 2005). In order to check the relevance of the use of microcalorimetry to quantify kinetic parameters, we use the already determined kinetic law of the reaction to calculate, solving the system of differential equations composed by relations 21 and 23, the reactional temperature or temperature difference which one should theoretically observe.…”

Section: Heat and Mass Balancesmentioning

confidence: 99%

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Simultaneous Thermodynamic and Kinetic Parameters Determination Using Differential Scanning Calorimetry

Frikha¹

2011

American Journal of Engineering and Applied Sciences

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Problem statement: The determination of reaction kinetics is of major importance, as for industrial reactors optimization as for environmental reasons or energy limitations. Although calorimetry is often used for the determination of thermodynamic parameters alone, the question that arises is: how can we apply the Differential Scanning Calorimetry for the determination of kinetic parameters. The objective of this study consists to proposing an original methodology for the simultaneous determination of thermodynamic and kinetic parameters, using a laboratory scale Differential Scanning Calorimeter (DSC). The method is applied to the dichromate-catalysed hydrogen peroxide decomposition. Approach: The methodology is based on operating of experiments carried out with a Differential Scanning Calorimeter. The interest of this approach proposed is that it requires very small quantities of reactants (about a few grams) to be implemented. The difficulty lies in the fact that, using such microcalorimeters, the reactants temperature cannot directly be measured and a particular calibration procedure has thus to be developed, to determine the media temperature in an indirect way. The proposed methodology for determination of kinetics parameters is based on resolution of the coupled heat and mass balances. Results: A complete kinetic law is proposed. The Arrhenius parameters are determined as frequency factor k₀ = 1.39×109 s−¹ and activation energy E = 54.9 kJ mol⁻¹. The measured enthalpy of reaction is ΔrH=−94 kJ mol⁻¹. Conclusion: The comparison of the results obtained by such an original methodology with those obtained using a conventional laboratory scale reactor calorimetry, for the kinetics determination of, shows that this new approach is very relevant

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“…Complexes of Cu(II) [25,26], Co(II) [27] and Fe(II) (Fenton's reagent) [28,29], bimetallic PtPd [30], dichromate salt [31] and aqua complexes [32] are also reported as promoters for this purpose.…”

mentioning

confidence: 99%

Catalytic activity of Schiff-base transition metal complexes supported on crosslinked polyacrylamides for hydrogen peroxide decomposition

Tamami

Ghasemi

2015

Journal of Organometallic Chemistry

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Study of the dichromate-catalysed hydrogen peroxide decomposition: Comparison of different batch mode reactors for the kinetics determination

Cited by 6 publications

References 8 publications

Predicting the Autoaccelerating Hydrogen Peroxide Decomposition Rate after Mixing with Sodium Hydroxide

Predicting the Autoaccelerating Hydrogen Peroxide Decomposition Rate after Mixing with Sodium Hydroxide

Simultaneous Thermodynamic and Kinetic Parameters Determination Using Differential Scanning Calorimetry

Catalytic activity of Schiff-base transition metal complexes supported on crosslinked polyacrylamides for hydrogen peroxide decomposition

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