Eterification of glycerol

Ing. Andrej TuranProf. Ing. Dušan Mravec, PhD.

Slovak University of TechnologyFaculty of Chemical and Food TechnologyDepartment of Organic Technology

Bio-fuels2010 => 5,75 %2020 => 10 %

FAME

FUELS

1/10 kg

Glycerol / FAME

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.

Influence of ethers of glycerol on fuels

OH

OH

OH

OH

OHO

R

+

OH

O

OH

R

H +

R

OHO

R

O

R

OH

O

R

OR

H +

+R

H +

O

OO

R

RR

R

- α-olefins (isobutylene), alcohols (tert-butylalcohol)

Main reactions

Side reaction

+R R RR

RR

+

Dewattines and Hinnekens, patent, 1994

Catalyst (Si/Al)

XG (%)DTBG

(mol %)TTBG

(mol %)

H-Beta (12,5) 97,5 54,6 0,2

H-Y (28) 98,9 60,4 6,4

p-Toluenesulfonic acid 97 60 9,4

H3PW12O40 98,9 54,1 8

Cs2HPW12O40 97,1 42,7 4,9

Amberlyst 15 98,5 47,1 6,4

Amberlyst 15 (crushed) 97,9 37,9 5,1

H-mordenit (11) 3,1 0 0

H-mordenit (100) 1,3 0 0

Isobutylene - Known facts from literature

Isobutylene - Known facts from literature

Catalyst (Si/Al)

XG (%) SDTBG,TTBG (%) References

Ar-SBA-15 100 92 1

H4SiW12O40 98 82 2

ionic liquid 100 93 2

Amberlyst 15 100 92 3

H730/ES70Y 100 97 3

1. Melero et al., Bioresource technology, 20112. Hee Jong Lee et al., Applied Catalysis A: General, 20103. Frusteri et al., Bioresource Technology, 2012

• 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 %

Resource X SDTBG, TTBG (%)

Isobuhtylene 100 88,7

C4 (44 w % IB) 18,8 20,1

C4 (20 w % IB) 2,9 14,2

• Hrivnák (Diploma thesis, 2011) - C4 fraction (20 w % IB), Amberlyst 35 Dry, X = 53 %, SG

DTBG,TTBG = 54 %

Isobutylene - Our research

• 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

• 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

•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 15 X = 90 %, SDDBG,TTBG = 28 %

tert-Butylalcohol - Known facts from literature

•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 %, SDTBG,TTBG = 15,6 %

tert-Butylalcohol - Our research

• 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

Pariente (Green chemistry, 2008):• Temperature 160°C• Amberlyst 35 (3 w % according to used glycerol)• EtOH:G = 15:1X = 52 %SME = 90 %

Melero (Bioresource technology,2011):• Temperature 200°C• Amberlyst 15 (19 w % according to used glycerol)• EtOH:G = 15:1X = 74 %S = 60 % (SME = 42 %)34 % - side products

Etanol - Known facts from literature

Aims of our future study

• Utilization of different lower alifatic alcohol • Utilization of bio-ethanol as etherification agent for preparation of glycerol ethers

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”