Masterproef
ingenieurswetenschappen
Master’s
thesis industriële
Industrial Sciences
Chemistry
The etherification of glycerol with tert. Butyl
ether to produce mono-glycerol tert. Butyl ether
Anke Zimmermann
Academiejaar:
Academic
year:
INTRODUCTION
2014-2015
RESULTS
The etherification of glycerol into oxygen rich compounds that can serve as octane enhancers
for fuel is an interesting way to make biodiesel viable.
Optimization
𝑌𝑖𝑒𝑙𝑑 = 19.63 + 4.79 ∙ 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 − 2.61 ∙ 𝑇𝑖𝑚𝑒 + 1.08 ∙ 𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑙𝑜𝑎𝑑𝑖𝑛𝑔
−1.45 ∙ 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 ∙ 𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑙𝑜𝑎𝑑𝑖𝑛𝑔 (𝐶𝑜𝑑𝑒𝑑 𝑣𝑎𝑙𝑢𝑒𝑠 𝑜𝑛𝑙𝑦)
Yield of m-GTBE in function of time and temperature (left) and in function of catalyst ratio and temperature (right)
Characteristics
Etherification of glycerol:
• With isobutene or tert. butyl alcohol (TBA),
• In presence of an acid catalyst (Amberlyst, Beta Zeolite) ,
• Mixture of m-, d- and t-GTBE.
59
1,6
57
55
53
51
49
47
1,4
1,2
1
0,8
0,6
0,4
0,2
0
45
EXPERIMENTAL
0
2,5
5
0
7,5
2,5
5
7,5
M-GTBE (%)
M-GTBE (%)
Step 4
Density for different % m-GTBE
Aim: determination of characteristics
gasoline with m-GTBE as additive
Characteristics:
- Octane number (ASTM D2699)
- Oxygen content (ASTM D4815)
- Vapor pressure (ASTM 3945)
- Density (ASTM D1298)
- Boiling range (ASTM D86)
Density (kg/m³)
Aim: optimization of etherification of
glycerol with tert. butyl alcohol
Parameters:
- Reaction time (2 - 6h)
- Temperature (80 - 110°C)
- Catalyst ratio relative to
glycerol mass (5 - 10%)
1,8
Oxygen content (wt%)
Vapor pressure (kPa)
m-GTBE is not investigated as gasoline additive yet,
despite its high octane number
Step 1
Oxygen content for different % m-GTBE
Vapor pressure for different % m-GTBE
61
740
738
736
734
732
730
728
726
724
722
720
718
0
2,5
5
7,5
M-GTBE (%)
Aim: isolation of m-GTBE from
GTBE-mixture
Methods:
-Normal distillation
-Vacuum distillation
Step 3
190
Aim: effect of blending of m-GTBE with
pure gasoline (mogas 92)
Percentages:
- 2,5 %
-5%
- 7,5 %
170
150
Temperature (oC)
Step 2
130
110
90
70
50
Pure gasoline
30
The etherification was carried out in a batch
reactor under 10 atm. N2.
IBP
Beta Zeolite was used as a catalyst.
10%
20%
30%
40%
50%
Volume%
60%
70%
2.5%
80%
90%
FBP
DISCUSSION AND CONCLUSIONS
REFERENCES:
1. K. Klepacovaa, D. Mravec and M. Bajus, "Tert-Butylation of glycerol catalysed by ion-exchange resins," Applied Catalysis : General, pp. 141-148, 2005.
2. R. Karinen and A. Krause, "New biocomponents from glycerol," Applied Catalysis, vol. 306, pp. 128-133, 2006.
3. R. Bell, "Zeolites," BZA: Promoting the Science of Nanoporous Materials, 2011. [Online]. Available: http://www.bza.org/zeolites/. [Accessed 15 May 2015].
Promotoren / Copromotoren:
Prof. Dr. Nguyen Hong Lien
Prof. Dr. Rita De Waele
•
Optimal yield of m-GTBE:
•
Commercial gasoline + m-GTBE:
high temperature (110°C)
low reaction time (2h)
low catalyst content (5%)
Temperatures higher than 110°C: more side reactions and lower conversion
positive effect on ignition characteristics
reduction of CO and hydrocarbon emissions