Eterification of glycerol

1. Slovak University of TechnologyFaculty of Chemical and Food Technology Department of Organic Technology Eterification of glycerol Ing. Andrej Turan Prof. Ing. Dušan Mravec, PhD.

2. Bio-fuels 2010=> 5,75 % 2020=> 10 % FAME 1/10 kg Glycerol / FAME FUELS

3. Influence of ethersofglycerol on fuels • Advantages • Improving of combustion, decreasing emission of solid particles, aldehydes, NOX and CO • Improving of low temperature characteristics of fuels (decreasing viscosity, cloud point, etc.) • Good solubility in diesel(DTBG, TTBG) • Disadvantages • Decreasing of oxidation stability (antioxidants) • Decreasing of flashpoint • Decreasing of cetane number (2-ethylhexyl nitrate) • Jaecker-Voirol et al., Oil & Gas Science and Technology, 2008.

4. Main reactions - α-olefins (isobutylene), alcohols (tert-butylalcohol)

5. Side reaction

6. Isobutylene - Known facts from literature Dewattines and Hinnekens, patent, 1994

7. Isobutylene - Known facts from literature Melero et al., Bioresource technology, 2011 Hee Jong Lee et al., Applied Catalysis A: General, 2010 Frusteri et al., Bioresource Technology, 2012

8. Isobutylene - Our research • Klepáčová et al. (Applied Catalysis A: General, 2005)(Applied Catalysis A: General 2007) -Amberlysts (15, 31, 35, 36, 39 and 119) and zeolites (H-Y and H-Beta) - Influence of temperature in range 50 – 90°C (kinetic study) • - Influence of solvent (dioxane sulfolane, dimethyl sulfoxide) • - Amberlyst 35 Dry, X = 100 %, SDTBG,TTBG = 88,7 % • Hrivnák (Diploma thesis, 2011) - C4 fraction (20 w % IB), Amberlyst 35 Dry,X = 53 %, SGDTBG,TTBG = 54 %

9. Suitable conditions for reaction • Pressure 1 – 2 MPa • Temperature 60 – 80°C • IB/G = 3:1 • Amount of catalyst 5 – 7,5 w % accordingto used glycerol • Durationof reaction 4 – 8 hours • Steering intensity(batch reactor) 1000-1300 min-1 • Catalyst Amberlyst (15, 35),

10. Aims of our future study • Using of C4 fraction as source of isobutylene • Using of strong acid catalysts to make all hydrocarbons in C4 useable as etherification agent • Study the preparation of glycerol ethers from rafined glycerol • Utilization of reaction products as solvent for etherification

11. tert-Butylalcohol - Known facts from literature • Ozbay et al. (International journal of Chemical Reactor Engineering, 2010)– comparison of different catalysts (Amberlyst15, 16, 35), Nafion-SAC-13, γ-Al2O3 - Amberlyst 15 (X = 50 %) • Frusteri (Applied Catalysis A: General, 2009)– Silica based catalysts, Nafion (SAC-13 and N-17) and Amberlyst 15X = 90 %, SDDBG,TTBG = 28 %

12. tert-Butylalcohol - Our research • Klepáčová (Petroleum and Coal, 2003) • (Applied Catalysis A: General, 2005) • (Chemical Papers, 2006) • Amberlysts (15, 35) H-Y and H-Beta • Influence of temperature, amount ofcatalyst, water • - Amberlyst 15, X = 86 %, SDTBG,TTBG = 15,6 %

13. Suitable conditions for reaction • Temperature 70°C • Pressure 0,1 MPa • TBA:G = 4:1 • Amount of catalyst 5 – 7,5 w % according to used glycerol • Duration of reaction 6 hours • Catalyst Amberlyst 15

14. Etanol - Known facts from literature • Pariente (Green chemistry, 2008): • Temperature 160°C • Amberlyst 35 (3 w % according to used glycerol) • EtOH:G = 15:1 • X = 52 % • SME = 90 % • Melero (Bioresource technology,2011): • Temperature 200°C • Amberlyst 15 (19 w % according to used glycerol) • EtOH:G = 15:1 • X = 74 % • S = 60 % (SME = 42 %) • 34 % - side products

15. Aims of our future study • Utilization of different lower alifatic alcohol • Utilization of bio-ethanol as etherification agent for preparation of glycerol ethers

16. Thank you for your attention Thiswork was supported by the Slovak Research and Development Agency under the contract No. APVV-0133-11. Founded by financial support of project No. HUSK/1101/1.2.1/0318 “Chemical Processes of Biomass Utilization in the Slovak-Hungarian Frontier Region”