Transformation of 2-Butene into Propene on WO3/MCM-48: Metathesis and Isomerization of n-Butene
Abstract
:1. Introduction
2. Results and Discussion
Analysis of Thermodynamics of n-Butene
3. Experimental Section
3.1. Preparation of Catalyst
3.2. Characterization of Catalysts
3.3. Test of Catalyst
3.4. Thermodynamic Analysis
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
- Zhang, D.Z.; Li, X.J.; Liu, S.L.; Zhu, X.X.; Chen, F.C.; Xu, L.Y. Investigations into the C4 olefin metathesis over Mo/Al2O3: Effects of support nature and pretreatment conditions on the product distribution. Appl. Catal. A Gen. 2014, 472, 92–100. [Google Scholar] [CrossRef]
- Calderon, N. Olefin metathesis reaction. Acc. Chem. Res. 1972, 5, 127–132. [Google Scholar] [CrossRef]
- Mahmood, C.S.; Yarmo, M.A.; Hamid, S.B.D.-A. Determination of active centres in Re2O7–Al2O3 metathesis catalysts by titration method. J. Mol. Catal. A Chem. 2000, 161, 11–16. [Google Scholar] [CrossRef]
- Li, X.; Zhang, W.; Liu, S.; Xie, S.; Zhu, X.; Bao, X.; Xu, L. Promoting effect of Mg in supported Mo/HBeta–Al2O3 catalyst for cross-metathesis of ethene and butene-2 to propene. J. Mol. Catal. A Chem. 2009, 313, 38–43. [Google Scholar] [CrossRef]
- Maksasithorn, S.; Praserthdam, P.; Suriye, K.; Devillers, M.; Debecker, D.P. WO3-based catalysts prepared by non-hydrolytic sol-gel for the production of propene by cross-metathesis of ethene and 2-butene. Appl. Catal. A Gen. 2014, 488, 200–207. [Google Scholar] [CrossRef]
- Zhao, Q.; Chen, S.-L.; Gao, J.; Xu, C. Effect of tungsten oxide loading on metathesis activity of ethene and 2-butene over WO3/SiO2 catalysts. Trans. Met. Chem. 2009, 34, 621–627. [Google Scholar] [CrossRef]
- Limsangkass, W.; Praserthdam, P.; Phatanasri, S.; Panpranot, J.; Chaemchuen, S.; Jareewatchara, W.; Ayudhya, S.K.N.; Suriye, K. Influence of micro- and nano-sized SiO2 excess support on the metathesis of ethylene and trans-2-butene to propylene over silica-supported tungsten catalysts. Reac. Kinet. Mech. Cat. 2014, 113, 225–240. [Google Scholar]
- Wu, J.-F.; Ramanathan, A.; Snavely, W.K.; Zhu, H.; Rokicki, A.; Subramaniam, B. Enhanced metathesis of ethylene and 2-butene on tungsten incorporated ordered mesoporous silicates. Appl. Catal. A Gen. 2016, 528, 142–149. [Google Scholar] [CrossRef]
- Hua, D.; Chen, S.-L.; Yuan, G.; Wang, Y.; Zhao, Q.; Wang, X.; Fu, B. Metathesis of butene to propene and pentene over WO3/MTS-9. Micropor. Mesopor. Mat. 2011, 143, 320–325. [Google Scholar] [CrossRef]
- Hua, D.; Chen, S.; Zhou, Z.; Lu, X.; Li, J. Poisoning Deactivation of Mesoporous Titanosilicate-Supported WO3 During Metathesis of Butene to Propene. Catal. Surv. Asia 2016, 20, 53–58. [Google Scholar] [CrossRef]
- Schalkwyk, C.V.; Spamer, A.; Moodley, D.J.; Dube, T.; Reynhardt, J.; Botha, J.M. Application of a WO3/SiO2 catalyst in an industrial environment: part I. Appl. Catal. A Gen. 2003, 255, 121–131. [Google Scholar] [CrossRef]
- Maksasithorn, S.; Debecker, D.P.; Praserthdam, P.; Panpranot, J.; Suriye, K.; Ayudhya, S.K.N. NaOH modified WO3/SiO2 catalysts for propylene production from 2-butene and ethylene metathesis. Chin. J. Catal. 2014, 35, 232–241. [Google Scholar] [CrossRef]
- Lwin, S.; Li, Y.; Frenkel, A.I.; Wachs, I.E. Nature of WOx Sites on SiO2 and Their Molecular Structure–Reactivity/Selectivity Relationships for Propylene Metathesis. ACS Catal. 2016, 6, 3061–3071. [Google Scholar] [CrossRef]
- Debecker, D.P.; Stoyanova, M.; Rodemerck, U.; Colbeau-Justin, F.; Boissère, C.; Chaumonnot, A.; Bonduelle, A.; Sanchez, C. Aerosol route to nanostructured WO3-SiO2-Al2O3 metathesis catalysts: Toward higher propene yield. Appl. Catal. A Gen. 2014, 470, 458–466. [Google Scholar] [CrossRef]
- Chaemchuen, S.; Phatanasri, S.; Verpoort, F.; Sae-ma, N.; Suriye, K. The structure-reactivity relationship for metathesis reaction between ethylene and 2-butene on WO3/SiO2 catalysts calcinated at different temperatures. Kinet. Catal. 2012, 53, 247–252. [Google Scholar] [CrossRef]
- Maksasithorn, S.; Praserthdam, P.; Suriye, K.; Debecker, D.P. Preparation of super-microporous WO3–SiO2 olefin metathesis catalysts by the aerosol-assisted sol–gel process. Micropor. Mesopor. Mat. 2015, 213, 125–133. [Google Scholar] [CrossRef]
- Jiang, W.; Huang, R.; Li, P.; Feng, S.; Zhou, G.; Yu, C.; Zhou, H.; Xu, C.; Xu, Q. Metathesis and isomerization of n-butene and ethylene over WO3/SiO2 and MgO catalysts: Thermodynamic and experimental analysis. Appl. Catal. A Gen. 2016, 517, 227–235. [Google Scholar] [CrossRef]
- Bhuiyan, T.I.; Arudra, P.; Akhtar, M.N.; Aitani, A.M.; Abudawoud, R.H.; Al-Yami, M.A.; Al-Khattaf, S.S. Metathesis of 2-butene to propylene over W-mesoporous molecular sieves: A comparative study between tungsten containing MCM-41 and SBA-15. Appl. Catal. A Gen. 2013, 467, 224–234. [Google Scholar] [CrossRef]
- Huang, S.; Chen, F.; Liu, S.; Zhu, Q.; Zhu, X.; Xin, W.; Feng, Z.; Li, C.; Wang, Q.; Xu, L. The influence of preparation procedures and tungsten loading on the metathesis activity of ethene and 2-butene over supported WO3 catalysts. J. Mol. Catal. A Chem. 2007, 267, 224–233. [Google Scholar] [CrossRef]
Samples | SBET (m2/g) | VP (cm3/g) | Average Pore Size (nm) | Total Acidity (mmol/g) |
---|---|---|---|---|
4 wt.%WO3/MCM-48 | 890.3 | 0.5376 | 2.590 | 0.1967 |
8 wt.%WO3/MCM-48 | 881.2 | 0.5409 | 2.544 | 0.2801 |
12 wt.%WO3/MCM-48 | 877.1 | 0.5243 | 2.578 | 0.2523 |
16 wt.%WO3/MCM-48 | 879.2 | 0.5299 | 2.557 | 0.4579 |
24 wt.%WO3/MCM-48 | 875.2 | 0.5137 | 2.524 | 0.4731 |
MCM-48(powder) | 1032.1 | 0.7296 | 2.701 | 0.0215 |
MCM-48(support) | 905.4 | 0.5639 | 2.601 | 0.0198 |
Samples | SBET (m2/g) | VP (cm3/g) | Average Pore Size (nm) | Total Acidity (mmol/g) |
---|---|---|---|---|
16 wt.%WO3/SiO2 | 341.8 | 0.7548 | 8.778 | 0.4133 |
16 wt.%WO3/MCM-41 | 822.6 | 0.5295 | 2.574 | 0.4431 |
16 wt.%WO3/MCM-48 | 879.2 | 0.5099 | 2.557 | 0.4579 |
Temperature (K) | Reactions | Log (K) | ||||
---|---|---|---|---|---|---|
633 | 2 | 10.51 | 11.06 | 3.504 | 0.5139 | |
3 | 8.412 | 10.505 | 1.761 | 0.7156 | ||
4 | C to C | −5.620 | −18.72 | 6.198 | −2.171 | |
C to T | −0.696 | 0.615 | −1.085 | 0.375 | ||
T to C | 0.665 | 1.229 | −0.113 | 0.039 | ||
T to T | −0.195 | 0.748 | −0.669 | 0.231 | ||
5 | B to C | 0.990 | −4.628 | 3.920 | −1.353 | |
B to T | 0.295 | −4.722 | 3.285 | −1.134 | ||
6 | C to P | −0.728 | 3.871 | −3.179 | 1.097 | |
T to P | −0.277 | 4.004 | −2.762 | 0.954 | ||
653 | 2 | 10.5 | 11.049 | 3.283 | 0.5643 | |
3 | 8.468 | 10.591 | 1.55 | 0.7517 | ||
4 | C to C | −5.946 | −19.318 | 6.671 | −2.232 | |
C to T | −0.696 | 0.616 | −1.098 | 0.367 | ||
T to C | 0.643 | 1.195 | −0.137 | 0.046 | ||
T to T | −0.210 | 0.725 | −0.684 | 0.229 | ||
5 | B to C | 0.980 | −4.463 | 4.013 | −1.343 | |
B to T | 0.299 | −4.714 | 3.379 | −1.131 | ||
6 | C to P | −0.721 | 3.882 | −3.257 | 1.090 | |
T to P | −0.235 | 3.991 | −2.842 | 0.951 | ||
673 | 2 | 10.49 | 11.034 | 3.062 | 0.578 | |
3 | 8.520 | 10.670 | 1.338 | 0.784 | ||
4 | C to C | −6.160 | −19.641 | 7.061 | −2.293 | |
C to T | −0.696 | 0.615 | −1.110 | 0.360 | ||
T to C | 0.621 | 1.161 | −0.161 | 0.052 | ||
T to T | −0.225 | 0.702 | −0.698 | 0.227 | ||
5 | B to C | 0.9710 | −4.657 | 4.106 | −1.333 | |
B to T | 0.301 | −4.712 | 3.473 | −1.128 | ||
6 | C to P | −0.714 | 3.892 | −3.334 | 1.083 | |
T to P | −0.244 | 3.797 | −2.922 | 0.949 | ||
693 | 2 | 10.48 | 11.02 | 2.842 | 0.610 | |
3 | 8.571 | 10.744 | 1.123 | 0.8229 | ||
4 | C to C | −6.393 | 19.981 | 7.457 | −2.351 | |
C to T | −0.6970 | 0.6130 | −1.122 | 0.3540 | ||
T to C | 0.6000 | 1.130 | −0.1840 | 0.05800 | ||
T to T | −0.2410 | 0.6790 | −0.7120 | 0.2240 | ||
5 | B to C | 0.9620 | −4.670 | 4.199 | −1.324 | |
B to T | 0.303 | −4.709 | 3.568 | −1.125 | ||
6 | C to P | −0.708 | 3.901 | −3.412 | 1.076 | |
T to P | −0.252 | 3.967 | −3.002 | 0.946 | ||
723 | 2 | 10.47 | 11.00 | 2.511 | 0.6585 | |
3 | 8.644 | 10.847 | 0.7990 | 0.8755 | ||
4 | C to C | −6.774 | −20.52 | 8.064 | −2.437 | |
C to T | −0.6990 | 0.6110 | −1.141 | 0.345 | ||
T to C | 0.5700 | 1.088 | −0.2170 | 0.066 | ||
T to T | −0.2630 | 0.6470 | −0.7320 | 0.221 | ||
5 | B to C | 0.9500 | −4.687 | 4.339 | −1.312 | |
B to T | 0.306 | −4.706 | 3.709 | −1.121 | ||
6 | C to P | −0.699 | 3.914 | −3.530 | 1.067 | |
T to P | −0.263 | 3.951 | −3.120 | 0.943 |
Content wt.% | |||||
---|---|---|---|---|---|
1 | 2 | 3 | 4 | 5 | |
W | 2.97 | 6.39 | 9.83 | 13.1 | 17.8 |
Si | 45.2 | 4205 | 40.7 | 38.7 | 36.1 |
Component | n-Butane | 1-Butene | Cis-2-Butene | Trans-2-Butene |
---|---|---|---|---|
Content (wt.%) | 11.50 | 6.99 | 24.8 | 56.71 |
© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Hua, D.; Zhou, Z.; Hua, Q.; Li, J.; Lu, X.; Xie, Y.; Xiao, H.; Li, M.; Yang, J. Transformation of 2-Butene into Propene on WO3/MCM-48: Metathesis and Isomerization of n-Butene. Catalysts 2018, 8, 585. https://doi.org/10.3390/catal8120585
Hua D, Zhou Z, Hua Q, Li J, Lu X, Xie Y, Xiao H, Li M, Yang J. Transformation of 2-Butene into Propene on WO3/MCM-48: Metathesis and Isomerization of n-Butene. Catalysts. 2018; 8(12):585. https://doi.org/10.3390/catal8120585
Chicago/Turabian StyleHua, Derun, Zheng Zhou, Qianqian Hua, Jian Li, Xinning Lu, Yongrong Xie, Hong Xiao, Mei Li, and Jin Yang. 2018. "Transformation of 2-Butene into Propene on WO3/MCM-48: Metathesis and Isomerization of n-Butene" Catalysts 8, no. 12: 585. https://doi.org/10.3390/catal8120585