Cu/Zn/Zr/Ga Catalyst for Utilisation of Carbon Dioxide to Methanol—Kinetic Equations

Hamryszak, Łukasz; Madej-Lachowska, M.; Grzesik, M.; Śliwa, Michał

doi:10.3390/catal12070757

Cited by 5 publications

(6 citation statements)

References 52 publications

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“…Common dynamic models include power law function model, [ 217,218 ] LH or Lewis‐Hotson‐Haggerty‐Wilhelm (LHHW) model, [ 219–221 ] and mechanism derivation model (Table 4). [ 222–225 ]…”

Section: Dynamicsmentioning

confidence: 99%

“…Hamryszak et al [ 221 ] studied the kinetics of methanol production from carbon dioxide over copper zinc zirconium gallium catalyst in a continuous phase fixed bed reactor. The dynamic model is as follows:

r_{1} goodbreak= k_{1} ([], \frac{P_{H_{2}}^{2} P_{{CO}_{2}} - \frac{P_{MeOH} P_{{normalH}_{2} O}}{K_{eq 1} P_{H_{2}}}}{{(1 + K_{H_{2}} P_{H_{2}} + K_{{CO}_{2}} P_{{CO}_{2}} + K_{MeOH} P_{MeOH} + K_{normalCO} P_{normalCO} + K_{{normalH}_{2} O} P_{{normalH}_{2} O})}^{3}})

r_{2} goodbreak= k_{2} ([], \frac{P_{H_{2}} P_{{CO}_{2}} - \frac{P_{normalCO} P_{{normalH}_{2} O}}{K_{normaleq 2}}}{{(1 + K_{H_{2}} P_{H_{2}} + K_{{CO}_{2}} P_{{CO}_{2}} + K_{MeOH} P_{MeOH} + K_{normalCO} P_{normalCO} + K_{{normalH}_{2} O} P_{{normalH}_{2} O})}^{2}})

…”

Section: Dynamicsmentioning

confidence: 99%

“…Common dynamic models include power law function model, [217,218] LH or Lewis-Hotson-Haggerty-Wilhelm (LHHW) model, [219][220][221] and mechanism derivation model (Table 4). [222][223][224][225] 3.1.1 | Power law function model Kobl et al [226] studied the reaction kinetics of carbon dioxide hydrogenation to methanol on CuZA and CuZZ catalysts.…”

Section: Dynamic Modelmentioning

confidence: 99%

“…Hamryszak et al [221] studied the kinetics of methanol production from carbon dioxide over copper zinc zirconium gallium catalyst in a continuous phase fixed bed reactor. The dynamic model is as follows:…”

Section: Lh Modelmentioning

confidence: 99%

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Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Wang,

Liu,

et al. 2023

Can J Chem Eng

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The process of preparing methanol from carbon dioxide is one of the ways to solve the environmental problems caused by greenhouse gases, the problem of fossil energy depletion, and the problem of fuel exhaust emissions. However, after decades of development, the process of preparing methanol from carbon dioxide is still unable to achieve large‐scale industrialization. This critical review sharply points out the problems and obstacles that need to be solved urgently on the industrialization road of carbon dioxide methanol preparation process and summarizes its progress. The problems faced by the methanol production industry from carbon dioxide are first the thermodynamic constraints, second the lower reaction rate and conversion effect, and finally the energy loss. In order to solve these problems, this paper first introduces the active sites, structural effects, and dynamic changes of copper‐based catalysts, as well as the unique reaction mechanism and doping modification of indium‐based catalysts. Zinc and zirconium promoters and some metal oxide supports can form unique interactions with active components to improve the catalytic performance of the catalyst. Next, various kinetic models and applications of methanol production from carbon dioxide are summarized, which is an important bridge linking laboratory and industrialization; the advantages and disadvantages of fixed bed reactor and paddle reactor were compared. Finally, the full text is summarized and prospected.

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Section: Dynamicsmentioning

confidence: 99%

r_{1} goodbreak= k_{1} ([], \frac{P_{H_{2}}^{2} P_{{CO}_{2}} - \frac{P_{MeOH} P_{{normalH}_{2} O}}{K_{eq 1} P_{H_{2}}}}{{(1 + K_{H_{2}} P_{H_{2}} + K_{{CO}_{2}} P_{{CO}_{2}} + K_{MeOH} P_{MeOH} + K_{normalCO} P_{normalCO} + K_{{normalH}_{2} O} P_{{normalH}_{2} O})}^{3}})

r_{2} goodbreak= k_{2} ([], \frac{P_{H_{2}} P_{{CO}_{2}} - \frac{P_{normalCO} P_{{normalH}_{2} O}}{K_{normaleq 2}}}{{(1 + K_{H_{2}} P_{H_{2}} + K_{{CO}_{2}} P_{{CO}_{2}} + K_{MeOH} P_{MeOH} + K_{normalCO} P_{normalCO} + K_{{normalH}_{2} O} P_{{normalH}_{2} O})}^{2}})

…”

Section: Dynamicsmentioning

confidence: 99%

Section: Dynamic Modelmentioning

confidence: 99%

“…Hamryszak et al [221] studied the kinetics of methanol production from carbon dioxide over copper zinc zirconium gallium catalyst in a continuous phase fixed bed reactor. The dynamic model is as follows:…”

Section: Lh Modelmentioning

confidence: 99%

See 2 more Smart Citations

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Wang,

Liu,

et al. 2023

Can J Chem Eng

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“…As mentioned above, the subjects of our investigation were oxides, as follows: ZnO, Ga 2 O 3 , and MgO. ZnO is a component of catalysts that are active in the production of hydrogen using ethanol [33], and in CO 2 conversion to methanol [34]. The first step of the reaction of ethanol is the formation of ethoxy groups by the reaction of alcohol with basic OH − and O 2− ; therefore, the recognition of the basicity of ZnO seems to be important for catalysis.…”

Section: Introductionmentioning

confidence: 99%

Basic Properties of ZnO, Ga2O3, and MgO—Quantitative IR Studies

Podobiński,

Datka

2024

Catalysts

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In our previous study, we elaborated a method of determination of concentrations of the basic sites O2− and OH− in a quantitative IR study of CO2 adsorption. Previous adsorption studies or TPD experiments only provided the total basicity without distinguishing between O2− and OH−. In this study, we determined the concentration of O2− and OH− on ZnO, Ga2O3, and MgO surfaces. The basicity of ZnO and MgO was found to be significantly higher than that of Ga2O3. The surface of ZnO was rich in O2−, the contribution of OH− was very small, and the Ga2O3 surface contained mainly OH−. For MgO, the contribution of O2− and OH− was comparable. According to the IR results, only a small fraction of all surface hydroxyls were sufficiently basic to react with CO2. The partial dehydroxylation changed the proportion of the concentrations of O2− and OH− on the oxides. We also elaborated upon a new method to determine the total concentration of basic sites via CO2 desorption monitored using IR. For all the oxides, we studied the sum of the concentrations of O2− and OH−, as determined in our quantitative IR studies, to find whether they were comparable with the total basicity determined in the desorption experiments.

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Kinetics of CO₂ hydrogenation to methanol over CuO/ZnO/ZrO₂ catalyst: Comparison of the differential and integral methods of kinetic analysis

Khawaja,

Usman

2024

Int J of Chemical Kinetics

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The experimental data over CuO/ZnO/ZrO2 catalyst for a wide range of operating conditions were used to develop the kinetics of the reaction CO2 hydrogenation to methanol. Three kinetic models such as the power law model, the Graaf kinetic model, and the Park kinetic model were tested against the experimental data. Both the mechanistic models have been developed based on the Langmuir‐Hinshelwood‐Hougen‐Watson approach and are specific only to the methanol synthesis from CO/CO2 hydrogenation. In an attempt to reduce the number of parameters in the two models, the abridged forms of these models were also tried. Overall, 25 kinetic rate equations were tested and the best‐fit kinetic rate expression with optimized parameters was worked out. Both the integral and differential methods of kinetic analysis were employed and their efficacy in finding the best‐fit expression was compared. The MATLAB built‐in function fminsearch was employed to perform the regression of the data. The Graaf model in its parent form, but with the new optimized values of the parameters, was found to be the best‐fit rate model. The Graaf kinetics, with re‐estimated parameters, could be helpful in designing and simulating a methanol synthesis reactor operating on CO2 and H2 feed and utilizing a CuO/ZnO/ZrO2 catalyst.

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Cu/Zn/Zr/Ga Catalyst for Utilisation of Carbon Dioxide to Methanol—Kinetic Equations

Cited by 5 publications

References 52 publications

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Basic Properties of ZnO, Ga2O3, and MgO—Quantitative IR Studies

Kinetics of CO₂ hydrogenation to methanol over CuO/ZnO/ZrO₂ catalyst: Comparison of the differential and integral methods of kinetic analysis

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Cu/Zn/Zr/Ga Catalyst for Utilisation of Carbon Dioxide to Methanol—Kinetic Equations

Cited by 5 publications

References 52 publications

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

Basic Properties of ZnO, Ga2O3, and MgO—Quantitative IR Studies

Kinetics of CO2 hydrogenation to methanol over CuO/ZnO/ZrO2 catalyst: Comparison of the differential and integral methods of kinetic analysis

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Product

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Kinetics of CO₂ hydrogenation to methanol over CuO/ZnO/ZrO₂ catalyst: Comparison of the differential and integral methods of kinetic analysis