Methanol Synthesis from Synthesis Gas utilziing an Innovated Ruthenium-Catalyzed Method
Veronica Ibe, Duncan Wass, Richard Wingad, Jason Lee, and Terence Nile
UNCG and University of Bristol
Abstract
Phosphorus NMRs of Ruthenium Catalyst (B)
Methanol can be synthesized from Syngas using ruthenium catalysts. We
report on the novel use of 3 new bidendate phosphinoamine ligands, to
probe the 2 steps believed to be involved with these catalysis. The first
step involves the formation of methyl formate from methanol using a base
and carbon monoxide. In the second step this methyl formate is
hydrogenated to give 2 moles of methanol. Reactions were done in a
single cell autoclave and products were analyzed via GC chromatography.
Conclusions of our studies will be reported as well as their relevance to the
catalytic reaction.
Results
Conclusions
Table 1: Concentration of MeOH and Formate of each catalytic run of
Hydrogenation of Methyl Formate with H2
Ligand
MeOH (mmol)
Formate (mmol)
21.1
2.8
20.4
2.7
25.2
3.3
Reaction Process
• Dimethyl: ~56.07 ppm
• Non-methyl: ~62.65 ppm
Table 2: Ratios of MeOH and Formate of each catalytic run of
Hydrogenation of Methyl Formate with H2
Ligand
MeOH %
• 3 Ruthenium Catalysts were made
• First part of the reaction (1 mole of MeOH to 1 mole of Formate) was
successfully conducted.
• Second part of the reaction (1 mole of Formate to 2 moles of Methyl
Formate) proved less successful.
• All 3 catalysts proved equally effective in the formation of methyl
formate.
• Catalyst (A) made the most MeOH in the formatin of MeOH from
Syngas reaction.
• Results are more qualitative due to the difficulties of measuring newly
made MeOH in contra to starting MeOH.
Formate %
Future
79.00%
• (1) 1 mole of Methanol is converted to methyl formate using Carbon
moxide and base NaOMe.
21.00%
79.00%
21.00%
79.40%
20.60%
• Attempt alternative experimental conditions:
- longer reflux time
- increase amount of catalyst used
- differing bases
- differing pressure
• (2) 1 mole of Methyl Formate is converted to 2 moles of Methanol using
hydrogen and Ruthenium Catalyst.
The extra mole of Methanol can be reused to restart the process.
Table 3: Concentration of MeOH and Formate of each catalytic run of
Syngas to MeOH
References
• (3) Exemplifies the combined reaction of reaction (1) and (2)
Hydrogenation of Methyl Formate
Ruthenium Catalysts
•
•
•
•
Ru Catalyst (0.01 mmol)
NaOMe (1 mmol) = 0.054 g
THF = 10 mL
Methyl Formate (20 mmol) = 1.23 mL
Ligand
MeOH (mmol)
Formate (mmol)
14.5
6.7
7.3
11.7
12.8
6.7
• S. Carobene, R.L. Wingad, D.F. Wass. Thesis. Cloning Methanol: A
Novel Ruthenium-Catalyzed Method for Methanol Synthesis from
Syngas via Methyl Formate. 2010
• E.S. Lee, K. Aika. Journal of Molecular Catalysis. 141. 241-248. 1999.
• L. Fan, Y. Sakaiya, K. Fujimoto. Applied Catalysis. 180. L11-L13. 1999
• S.P. Tanner, D.L. Trimm, M.S. Wainwright. Journal of Molecular
Catalysis. 18. 215-222. 1999
Duration: 1 hour
Temperature: 100° C
H2 50 bar
Syngas to Methanol
(A)
(B)
•
•
•
•
Ru Catalyst (0.01 mmol)
NaOMe (1 mmol) = 0.054g
THF = 10 mL
MeOH (20 mmol) = 0.81 mL
Duration: 24 hours
Temperature: 100° C
H2/CO 50 bar
(C)
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Acknowledgements
Thanks to Dr. Duncan Wass, Richard L. Wingad, Jason Lee, and Terrence
A. Nile.
Thanks to University of Bristol.
Special thanks to the financial support from the National Science
Foundation (grant 0964420) is gratefully acknowledged.