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Kinetics of Reduction of NiO-WO3 Mixtures by Hydrogen
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Process Science.
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Process Science.
2010 (English)In: Metallurgical and materials transactions. B, process metallurgy and materials processing science, ISSN 1073-5615, E-ISSN 1543-1916, Vol. 41, no 1, 161-172 p.Article in journal (Refereed) Published
Abstract [en]

The kinetics of reduction of the oxide mixtures of Ni-W with different Ni/(Ni-W) molar ratios within the range of 923 K to 1173 K in flowing hydrogen gas was investigated by means of thermogravimetric analysis under isothermal conditions. The products were examined by X-ray diffraction, scanning electron microscope (SEM), and electron dispersion spectroscopy (EDS) analyses. Five different oxide mixtures apart from the pure oxides were studied in the present work. The results indicate that the reduction reaction proceeds through three consecutive steps that are as follows: NiO-WO3 -> Ni-WO3 -> Ni-WO2 -> Ni-W From the experimental results, the Arrhenius activation energies of the three steps were evaluated for all of the studied compositions. The activation energy for the first step was calculated to be approximately 18 kJ/mol. For the second and third stages, the activation energy values varied from 62 to 38 kJ/mol for the second stage and 51 to 34 kJ/mol for the third stage depending on the Ni/(Ni + W) molar ratio in the precursors; the activation energy increased with increasing ratios. SEM images showed that the grain size of the final product was dependent on the Ni/(Ni + W) molar ratio; smaller grains were formed at higher nickel contents.

Place, publisher, year, edition, pages
2010. Vol. 41, no 1, 161-172 p.
Keyword [en]
nickel oxide, alloys, tungstate, gas
National Category
Materials Engineering
Identifiers
URN: urn:nbn:se:kth:diva-19365DOI: 10.1007/s11663-009-9302-7ISI: 000276235900017Scopus ID: 2-s2.0-77951297719OAI: oai:DiVA.org:kth-19365DiVA: diva2:337412
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Investigations of the Kinetics of Reduction and Reduction/Carburization of NiO-WO3 Precursors.
Open this publication in new window or tab >>Investigations of the Kinetics of Reduction and Reduction/Carburization of NiO-WO3 Precursors.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Kinetic studies of reduction of the mixtures of NiO and WO3 having different Ni/(Ni+W) molar ratios in flowing hydrogen gas were investigated by means of Thermo Gravimetric Analysis (TGA), Fluidized Bed (FB) technique as well as Thermal diffusivity measurements under isothermal conditions. In the case of TGA, the reaction progress was monitored by mass loss, while evolved gas analysis by a gas chromatograph was the indicator of the reaction progress in the case of FB. The results indicate that the reduction reaction proceeds through three consecutive steps, viz.

NiO-WO3 Ni-WO3 Ni-WO2 Ni-W

The present results show that the fluidized bed technique can be successfully utilized in bulk production of intermetallics containing W and a transition metal (or a composite material) wherein the process conditions would have a strong impact on the particle size of the end product.

During the investigations, it was found that there was a delay in the reaction during the hydrogen reduction of NiO-WO3 mixed oxides in a fluidized bed reactor. In order to understand the same, a theoretical model was developed to estimate the apparent reaction rate constant for the reduction reaction from the intrinsic chemical reaction rate constant. Appropriate differential mass balance equations based on intrinsic chemical reaction rate constants and thermodynamic equilibria were developed. The proposed model was successfully applied in predicting the overall reaction kinetics of a fluidized bed reactor. This model is also suitable for scale-up calculations.

SEM images showed that the particle size of the final product was dependent on the Ni/(Ni+W) molar ratio; smaller particles were formed at higher nickel contents. X-ray diffractions of the reduced precursors exhibited slight shift of Ni peaks from the standard one indicating the dissolution of W into Ni.

A new method for studying kinetics of the hydrogen reduction of NiO-WO3 precursors was developed in which the reaction progress was monitored by following the change of thermal diffusivity of the precursors. Activation energies of reduction as well as sintering were calculated. This method is considered unique as it provides information regarding the physical changes like sintering, change of porosity and agglomeration along with the chemical changes occurring during the gas/solid reaction.

As a continuation of the kinetic studies, Ni-W-C ternary carbides were synthesized by simultaneous reduction–carburization of Ni-W-O system using H2-CH4 gas mixtures by TGA. The results showed that the reduction of the oxide mixture was complete before the carburization took place. The nascent particles of the metals formed by reduction could react with the gas mixture with well-defined carbon potential to form a uniform product of Ni-W-C. The above-mentioned experiments were conducted in such a way to ensure that the reaction was controlled by the chemical reaction. The activation energies of the reduction as well as carburization processes at different stages were calculated accordingly.

The present dissertation demonstrates the potential of the investigations of gas/solid reactions towards tailoring the process towards materials with optimized properties as for example introduction of interstitials. The present process design is extremely environment-friendly with reduced number of unit processes and the product being H2O.

Place, publisher, year, edition, pages
Stockholm: KTH, 2010. viii, 54 p.
Keyword
Reduction, Reduction-Carburization, Gas-solid Reactions, Kinetics, Hydrogen, Methane, Thermogravimetric analysis, Fluidized bed, Simulation, Thermal diffusivity, Thermal conductivity, Laser flash
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-26015 (URN)KTH/MSE--10/51--SE+THMETU/AVH (ISRN)978-91-7415-774-1 (ISBN)
Public defence
2010-11-25, Salongen Lavoisier, Biblioteket, Osquars Backe 31, KTH, Stockholm, 09:00 (English)
Opponent
Supervisors
Note
QC 20101112Available from: 2010-11-12 Created: 2010-11-09 Last updated: 2012-03-23Bibliographically approved

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