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

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

3. Advantages Improving of combustion, decreasing emission of solid particles, aldehydes, NO X 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. Influence of ethers of glycerol on fuels

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

5. Side reaction

6. Dewattines and Hinnekens, patent, 1994 Catalyst (Si/Al) X G (%) DTBG (mol %) TTBG (mol %) H-Beta (12,5)97,554,60,2 H-Y (28)98,960,46,4 p-Toluenesulfonic acid97609,4 H 3 PW 12 O 40 98,954,18 Cs 2 HPW 12 O 40 97,142,74,9 Amberlyst 1598,547,16,4 Amberlyst 15 (crushed)97,937,95,1 H-mordenit (11)3,100 H-mordenit (100)1,300 Isobutylene - Known facts from literature

7. Catalyst (Si/Al) X G (%) S DTBG,TTBG (%) References Ar-SBA-15100921 H 4 SiW 12 O 40 98822 ionic liquid100932 Amberlyst 15100923 H730/ES70Y100973 1.Melero et al., Bioresource technology, 2011 2.Hee Jong Lee et al., Applied Catalysis A: General, 2010 3.Frusteri et al., Bioresource Technology, 2012

8. 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 %, S DTBG,TTBG = 88,7 % ResourceXS DTBG, TTBG (%) Isobuhtylene10088,7 C4 (44 w % IB)18,820,1 C4 (20 w % IB)2,914,2 Hrivnák ( Diploma thesis, 2011 ) - C4 fraction (20 w % IB), Amberlyst 35 Dry, X = 53 %, S G DTBG,TTBG = 54 % Isobutylene - Our research

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

10. 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 Aims of our future study

11. Ozbay et al. ( International journal of Chemical Reactor Engineering, 2010 ) – comparison of different catalysts (Amberlyst15, 16, 35), Nafion-SAC-13, γ -Al 2 O 3 - Amberlyst 15 (X = 50 %) Frusteri ( Applied Catalysis A: General, 2009 ) – Silica based catalysts, Nafion (SAC-13 and N-17) and Amberlyst 15 X = 90 %, S DDBG,TTBG = 28 % tert-Butylalcohol - Known facts from literature

12. 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 of catalyst, water - Amberlyst 15, X = 86 %, S DTBG,TTBG = 15,6 % tert-Butylalcohol - Our research

13. 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 Suitable conditions for reaction

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

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 This work 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”