Effect of Cesium and Phosphate Addition to Mo/V/W Mixed Oxide Catalysts for the Gas Phase Oxidation of Methacrolein to Methacrylic Acid
Abstract
:1. Introduction
2. Results and Discussion
2.1. Catalysts A, B and C Containing Cs/P ≈ 1
2.2. Catalyst A with Varied Cs/P and (Mo + V + W)/P Ratios
2.3. Evaluating the Catalyst Performance
2.4. Catalyst Stability
3. Experimental
3.1. Catalyst Preparation
3.2. Reaction Unit
3.3. Catalyst Characterization
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Nomenclature
Abbreviations | |
FID | flame ionization detector |
HAc | acetic acid |
HPA | heteropoly acid |
MAA | methacrylic acid |
MAC | methacrolein |
MO | mixed oxide |
TCD | thermal conductivity detector |
wt | weight |
Symbols | |
ABET | specific surface area (m2∙g−1) |
CMAC,s | MAC concentration on the catalyst surface (mol∙m−3) |
CMAC,g | MAC concentration in the gas phase (mol∙m−3) |
dHPA | Unit cell parameter of HPA phase (nm) |
Fi | integrated area in XRD diffractogram (−) |
kF,i | surface specific reaction rate coefficient (m∙s−1) |
km,I | mass specific reaction rate coefficient (m3∙kg−1∙s−1) |
molar flow of component i (mol∙s−1) | |
molar flow of component i at the inlet (mol∙s−1) | |
p | pressure (bar) |
RSi | carbon-based reactor selectivity to component i (−) |
T | temperature (°C) |
TOS | time on stream (h) |
total volumetric inlet flow (m3∙s−1) | |
Wz | Weisz number for inner mass transfer limitation (−) |
Xi | conversion of component i (−) |
zi | carbon number of component i (−) |
τmod | modified residence time at standard conditions (kg∙s∙m−3) |
Subscripts | |
0 | inlet condition |
c | corner sharing |
cat | catalyst |
e | edge sharing |
i | component i |
max | maximum |
N | Norm conditions (0 °C, 1.01325 bar) |
t | terminal |
Superscripts | |
R | reactor |
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Catalyst | Chemical Composition | ABET (m2/g) | Cryst. (wt.%) | h-Phase (wt.%) * | M1 (wt.%) * | HPA (wt.%) * |
---|---|---|---|---|---|---|
A | Mo8.0V2.0W1.0 | 13.9 | ≈79 | >95 | <5 | 0 |
B | Mo8.0V2.0W0.5 | 20.6 | ≈68 | ≈55 | ≈45 | 0 |
C | Mo8.0V2.3W0.8 | 25.8 | ≈58 | <5 | >95 | 0 |
A_Cs0.6P0.6 | Mo8.0V2.0W0.9Cs0.6P0.6 | 8.8 | ≈71 | <5 | ≈0 | >95 |
B_Cs0.5P0.6 | Mo8.0V2.5W0.5Cs0.5P0.6 | 15.3 | ≈65 | 0 | ≈25 | ≈75 |
C_Cs0.5P0.5 | Mo8.0V2.4W0.8Cs0.5P0.5 | 24.9 | ≈62 | 0 | ≈60 | ≈40 |
Catalyst | Chemical Composition | Cryst. (wt.%) | h-phase (wt.%) * | HPA (wt.%) * | ABET (m2/g) |
---|---|---|---|---|---|
A | Mo8.0V2.0W1.0 | ≈78 | 100 | 0 | 11.6 |
A_Cs0.3P0.3 | Mo8.0V2.0W0.9Cs0.3P0.2 | ≈72 | 55 | 45 | 9.4 |
A_Cs0.4P0.4 | Mo8.0V2.0W1.0Cs0.4P0.4 | ≈75 | 40 | 60 | 7.4 |
A_Cs0.5P0.5 | Mo8.0V2.0W1.0Cs0.5P0.5 | ≈72 | 25 | 75 | 9.0 |
A_Cs0.6P0.6 | Mo8.0V2.0W0.9Cs0.6P0.6 | ≈71 | 5 | 95 | 8.8 |
A_Cs0.7P0.7 | Mo8.0V2.0W0.9Cs0.7P0.7 | ≈75 | 0 | 100 | 9.5 |
Catalyst | Chemical Composition | Cryst. (wt.%) | h-Phase (wt.%) * | HPA (wt.%) * | dHPA (nm) | ABET (m2/g) |
---|---|---|---|---|---|---|
A_P0.3 | Mo8.0V2.0W1.0P0.3 | ≈77 | 60 | 40 | 1.168 | 6.7 |
A_Cs0.3P0.3 | Mo8.0V2.0W0.9Cs0.3P0.2 | ≈72 | 65 | 45 | 1.173 | 9.4 |
A_Cs0.6P0.3 | Mo8.0V2.0W0.9Cs0.7P0.3 | ≈73 | 40 | 60 | 1.179 | 11.4 |
A_P0.5 | Mo8.0V2.0W1.0P0.5 | ≈73 | 40 | 60 | 1.170 | 5.2 |
A_Cs0.5P0.5 | Mo8.0V2.0W1.0Cs0.5P0.5 | ≈72 | 25 | 75 | 1.174 | 9.0 |
A_Cs1.0P0.5 | Mo8.0V2.0W1.0Cs0.9P0.5 | ≈79 | 20 | 80 | 1.178 | 10.8 |
Catalyst | Ageing State | dHPA (nm) | ABET (m2∙g−1) |
---|---|---|---|
A_Cs0.5P0.5 | Fresh state | 1.175 | 8.21 |
A_Cs0.5P0.5 | 0.5 molMAC/gKat | 1.186 | 9.52 |
A_Cs0.5P0.5 | 1.0 molMAC/gKat | 1.189 | 10.76 |
Parameter | Value |
---|---|
isothermal reactor temperature (°C) | 300/340 * |
methacrolein (MAC) content in the feed (% v/v) | 3.4 |
molar feed ratio MAC:O2 | 1:2 |
water vapor content (% v/v) | 21 |
total pressure (bar(a)) | 1.5 |
total volumetric inlet flow (mLN/min) | 150–1200 |
modified residence time (kg·s/m3) | 500–8000 |
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Sennerich, M.; Weidler, P.G.; Heißler, S.; Kraushaar-Czarnetzki, B. Effect of Cesium and Phosphate Addition to Mo/V/W Mixed Oxide Catalysts for the Gas Phase Oxidation of Methacrolein to Methacrylic Acid. Catalysts 2021, 11, 231. https://doi.org/10.3390/catal11020231
Sennerich M, Weidler PG, Heißler S, Kraushaar-Czarnetzki B. Effect of Cesium and Phosphate Addition to Mo/V/W Mixed Oxide Catalysts for the Gas Phase Oxidation of Methacrolein to Methacrylic Acid. Catalysts. 2021; 11(2):231. https://doi.org/10.3390/catal11020231
Chicago/Turabian StyleSennerich, Maximilian, Peter G. Weidler, Stefan Heißler, and Bettina Kraushaar-Czarnetzki. 2021. "Effect of Cesium and Phosphate Addition to Mo/V/W Mixed Oxide Catalysts for the Gas Phase Oxidation of Methacrolein to Methacrylic Acid" Catalysts 11, no. 2: 231. https://doi.org/10.3390/catal11020231