Selective Hydrogenation of 2-Methyl-3-butyn-2-ol in Microcapillary Reactor on Supported Intermetallic PdZn Catalyst, Effect of Support Doping on Stability and Kinetic Parameters
Abstract
:1. Introduction
2. Results and Discussion
2.1. Structural and Composition Analysis of Catalysts and Coatings
2.2. Hydrogenation of 2-Methyl-3-butyn-2-ol on PdZn/TixM1−xOy Coatings in a Microcapillary Reactor
2.3. Hydrogenation of 2-Methyl-3-butyn-2-ol on PdZn/TixM1−xOy Coatings after Different Pretreatments
3. Materials and Methods
3.1. Synthesis of PdZn/TixM1−xO2 (M = Zr, Ce, Zn) Coatings
3.2. Investigation of the Physicochemical Properties of TixM1−xO2 Composites (M = Zr, Ce, Zn) and PdZn/Tix Zr1−xO2 Catalysts and Coatings
3.3. Catalytic Tests
3.4. Calculations of Kinetic Parameters
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Supports | Calcination Temperature, K | Specific Surface Area, m2/g | Pore Size, nm | Pore Volume, cm3/g | Crystallite Size, nm |
---|---|---|---|---|---|
TiO2 | 673 | 151.8 | 3.8 | 0.132 | 6 |
TiO2 | 873 | 23.4 | 10.2 | 0.061 | 22 |
Ti0.95Ce0.05O2 | 673 | 261.4 | 4.0 | 0.22 | amorphous |
Ti0.95Ce0.05O2 | 873 | 57.5 | 8.9 | 0.144 | 9 |
Ti0.80Zr0.20O2 Ti0.80Zr0.20O2 | 673 | 185.5 | 3.6 | 0.084 | 9 |
873 | 128.6 | 5.9 | 0.236 | 15 | |
Ti0.80Zn0.20O1.8 Ti0.80Zn0.20O1.8 | 673 | 250.9 | 4.2 | 0.253 | amorphous |
873 | 51 | 13.5 | 0.217 | 25 |
Sample | MBY Concentration, t=28, mol/L | Q, t = 28, gMBE/day | A, t = 28, gMBE/s/gPd | S97, t = 28 % | MBY Concentration, t = 88, mol/L | Q, t = 88, gMBE/day | A, t = 88, gMBE/s/gPd | S97, t = 88 % |
---|---|---|---|---|---|---|---|---|
PdZn/TiO2 | 0.8 | 3.6 | 1.5 | 96.7 | 2.2 | 4.1 | 1.3 | 97.6 |
PdZn/Ti0.8Zr0.2O2 | 1.0 | 6.3 | 1.4 | 96.8 | 2.0 | 12.0 | 2.6 | 93.4 |
PdZn/Ti0.95Ce0.05O2 | 1.0 | 3.6 | 1.8 | 93.7 | 2.0 | 2.9 | 1.4 | 96.3 |
PdZn/Ti0.8Zn0.2O2 | 0.4 | 0.43 | 0.12 | 97.6 | 1.0 | 1.56 | 0.41 | 98.0 |
Parameter | PdZn/TiO2 | PdZn/Ti0.8Zr0.2O2 | PdZn/Ti0.95Ce0.05O2.08 | PdZn/Ti0.8Zn0.2O1.8 |
---|---|---|---|---|
k1’/mol/L/s/gPd | 714 | 788 | 1258 | 186 |
k2’mol/L/s/gPd | 132 | 176 | 941 | 14 |
k3’/mol/L/s/gPd | 20 | 41 | 0.0001 | 5 |
KMBY/L/mol | 61 | 43 | 30 | 56 |
KMBE/L/mol | 0.8 | 0.6 | 1 | 0.3 |
KMBA/L/mol | 8 | 0.01 | 0.001 | 1 |
KMBE/KMBY | 0.013 | 0.014 | 0.031 | 0.005 |
KMBA/KMBE | 10 | 0.017 | 0.001 | 3.3 |
KMBA/KMBY | 0.13 | 2.3 × 10−4 | 3.3 × 10−5 | 0.02 |
σMBY, % | 25.0 | 7.5 | 24.0 | 3.3 |
σMBE, % | 5.3 | 3.7 | 3.9 | 0.8 |
σMBA, % | 13.0 | 8.0 | 11.6 | 20.7 |
Q, gMBE/day | 3.6 | 6.3 | 3.6 | 0.42 |
S97,% | 96.7 | 96.8 | 93.7 | 97.5 |
Catalyst | Pretreatment | Pd3d5/2 | Zn2p3/2 | Ce3d5/2 | Pd/Ti | Pd/Zn | At. Conc. C, % | At. Conc. Zn,% |
---|---|---|---|---|---|---|---|---|
PdZn/TiO2 | H2/Ar, 573 K, 2 h | 335.1 | 1022 | - | 0.005 | 0.17 | 52.4 | 0.31 |
PdZn/TiO2 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 335.3 | 1022.3 | - | 0.006 | 0.21 | 26.1 | 0.53 |
PdZn/Ti0.95Ce0.05O2 | H2/Ar, 573 K, 2 h | 335.1 | 1022 | 882.3 | 0.006 | 2.0 | 50.9 | 0.04 |
PdZn/Ti0.95Ce0.05O2 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 335.3 | 1022.2 | 882.2 | 0.009 | 2.3 | 32.1 | 0.07 |
PdZn/Ti0.8Zn0.2O1.8 | H2/Ar, 573 K, 2 h | 335.1 | 1022.3 | - | 0.003 | 0.005 | 43.3 | 5.84 |
PdZn/Ti0.8Zn0.2O1.8 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 335.2 | 1022.3 | - | 0.004 | 0.007 | 26.3 | 7.2 |
Catalyst | Pretreatment | Pd(0) (%) | PdZn (%) | Pd(II) (%) |
---|---|---|---|---|
PdZn/TiO2 | H2/Ar, 573 K, 2 h | 48.9 | 23.6 | 27.5 |
PdZn/TiO2 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 50.5 | 27.6 | 21.9 |
PdZn/Ti0.95Ce0.05O2 | H2/Ar, 573 K, 2 h | 60.3 | 19.5 | 20.2 |
PdZn/Ti0.95Ce0.05O2 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 46.1 | 18.1 | 35.8 |
PdZn/Ti0.8Zn0.2O1.8 | H2/Ar, 573 K, 2 h | 52.6 | 36.0 | 11.4 |
PdZn/Ti0.8Zn0.2O1.8 | Air, 573 K, 2 h, H2/Ar, 573 K, 2 h | 58.1 | 31.8 | 10.1 |
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Okhlopkova, L.; Prosvirin, I.; Kerzhentsev, M.; Ismagilov, Z. Selective Hydrogenation of 2-Methyl-3-butyn-2-ol in Microcapillary Reactor on Supported Intermetallic PdZn Catalyst, Effect of Support Doping on Stability and Kinetic Parameters. Catalysts 2022, 12, 1660. https://doi.org/10.3390/catal12121660
Okhlopkova L, Prosvirin I, Kerzhentsev M, Ismagilov Z. Selective Hydrogenation of 2-Methyl-3-butyn-2-ol in Microcapillary Reactor on Supported Intermetallic PdZn Catalyst, Effect of Support Doping on Stability and Kinetic Parameters. Catalysts. 2022; 12(12):1660. https://doi.org/10.3390/catal12121660
Chicago/Turabian StyleOkhlopkova, Lyudmila, Igor Prosvirin, Mikhail Kerzhentsev, and Zinfer Ismagilov. 2022. "Selective Hydrogenation of 2-Methyl-3-butyn-2-ol in Microcapillary Reactor on Supported Intermetallic PdZn Catalyst, Effect of Support Doping on Stability and Kinetic Parameters" Catalysts 12, no. 12: 1660. https://doi.org/10.3390/catal12121660