Dr. Sanjeev P. Maradur Asst. Prof, Materials Science Division

1. Biorefineries World Biodiesel Congress & Expo December 5, 2016 Etherification of bio-glycerol to oxygenated fuel additive over sulfonated mesoporous polymer catalyst Dr. Sanjeev P. Maradur Asst. Prof, Materials Science Division Poornaprajna Institute of Scientific Research Devanahalli, Bangalore, Karnataka, India.

2. Overview • Introduction • Methodology • Catalyst Screening • Summary and Conclusion

3. Introduction • The booming biodiesel and oleochemicals manufacturing taking place worldwide • Vegetable oils and animal fats are hydrolyzed to make oleochemicals, or transesterified to produce biodiesel. • This unique situation has led to consistently low glycerol prices • The triol is liberated at slightly more than 10% by weight of triglycerides level either in the hydrolytic synthesis of fatty acids (soap), and in the transesterification of oils and fats with methanol to make biodiesel

4. PROCESSES FOR BIODIESEL MANUFACTURE • Homogeneous: Commercial. NaOH; 65°C; water and acid washes; yields alkyl esters and glycerol. • Enzymatic: Lipase; cost of enzyme is a major barrier. Enzyme denatures in the presence of methanol; requires additional solvent THF or hexane. • Heterogeneous:Zn aluminates (Axens), Ca-carbonate, microporous titaniosilicates, sulfated/tungstated zirconia. “Advances in Biodiesel Production: Processes and Technologies “ edited by R Luque, J A Melero, Woodhead Publishing Series in Energy

5. LURGI’S BIODIESEL PROCESS http://www.jj-lurgi.com/doc/Methylester(Biodiesel)

6. Indian Senario: Energy Sector • COAL • CRUDE PETROLEUM: Through Imports • NATURAL GAS: Recent explorations within the country • BIODIESEL: National Policy on Biofuels , Government of India

7. Indian BioFuel Policy • The Minimum Purchase Price (MPP) for bio-diesel by the Oil Marketing Companies (OMCs) will be linked to the prevailing retail diesel price. • Financial incentives, including subsidies and grants, may be considered upon merit for new and second generation feed stocks, advanced technologies and conversion processes, and production units based on new and second generation feed stocks. • Bio-ethanol already enjoys concessional excise duty of 16% and biodiesel is exempted from excise duty. No other Central taxes and duties are proposed to be levied on bio-diesel and bio-ethanol.

8. Glycerol Transformations Petroleum based

9. Catalytic etherification of glycerol to produce tert-butyl ethers of glycerol

10. Uses of Glycerol tert-butyl ethers • Glycerol ethers reduces the viscosity of the fuel upon blending • It increases cold flow properties of the fuel • It also provides the required flash point • It increases the oxidation stability of the fuel • Glycerol ethers when blended with commercial diesel reduces the soot and NOx particulate emissions Or / tert-Butanol Boskurt et al. Fuel Processing Technology, 2015, 138, 780-804

11. Literature Review Reference: Gonzalez et al, Appl. Catal. A: Gen., 2013, 450, 178–188, Patrícia A. Celdeira et al, Appl. Catal. A: Gen., 2014, 478, 98-106

12. Associated Problems of the Reaction System • Water produced as a byproduct can adsorb on the active centers of catalyst, resulting in partial deactivation of catalyst due to competition with the alcohol reactant species. • Sulfonated resins are good acidic catalysts, but their shortcomings such as low surface area and low stability are still challengeable (Amberlyst-15).

13. Mesoporous Polymer • A new class of advanced materials, which share the advantages of both mesostructured materials and polymers of organic frameworks. • A variety of useful organic functional groups by grafting or co-condensation. • Contain a high crosslink density together with mesopores, and exhibit important properties such as high surface area (up to 600 m2 g‑1). • Ability to sorb reactants in both thermodynamically good and poor solvents

14. Advantages of Mesoporous Polymers • High catalytic activity and life time in terms of stability and recycling may be expected for mesoporous as compared to conventional polymeric resins • Proper balance of hydrophobicity-hydrophilicity in mesoporous polymers may result in high catalytic activity and high selectivity especially in the reactions where water is formed as by-product/reagent/solvent itself

15. Methodology Catalyst Synthesis

16. Catalyst preparation Preparation of Mesoporous PDVB Step -1 Divinyl benzene + AIBN (Azobisisobutyronitrile) + THF + water Stirring at room temperature for 3 h Hydrothermal treatment at 100 oC for 2days Final polymer dried at room temperature Polymer in cylindrical shape

17. Step -2 Sulphonation of Mesoporous PDVB Crushed Mesoporous PDVB were out-gassed at 100oC for 3h 1.5 g of crushed Mesoporous PDVB + 30 ml CH2Cl2 70 ml of conc. H2SO4 + Ag2SO4 (20 mg) Heated under stirring for x time, filtered and washed with distilled water till neutral pH Mesoporous PDVB-X-SO3H Fujian Liu et al, J. Catal., 2010,271, 52–58

18. The textural and acidic properties of various solid acid catalysts a = from t-plot method b = from pore size distribution by BJH method c = Measured by acid- base titration d = from the manufacturer e = from TPD-NH3 Entries marked in red are standard samples used as received from suppliers

19. Thermal Stability of the synthesized Polymers 25 -110oC, Water molecule. 210 -380oC, Sulfonic group. 420-530oC, Destruction of organic ramework.

20. Catalytic activity of mesoporous polymer and other solid acid catalysts for glycerol etherification Reaction condition: Glycerol: tert-butanol=1:4, (6g of glycerol + 19.3g of tert-butanol), Catalyst = 0.30 g, Temp = 95 oC. TON= moles of glycerol converted per mole of acid site

21. Catalytic activity of MP-SO3 H-x catalysts containing different amount of acidity

22. Effect of Reaction Temperature wt % Reaction condition: Glycerol: tert-butanol=1:4, (Glycerol = 6g , tert-butanol = 19.3g), M-PDVB-8 catalyst = 0.30 g, Time = 6 h Temp (oC)

23. Effect of Reactants Mole Ratio Reaction condition: Glycerol: tert-butanol=1:6, M-PDVB-8 Catalyst = 0.30g, Temp = 95 oC.

24. Effect of Catalyst Concentration Reaction condition: Glycerol: tert-butanol=1:6, (4.5g of glycerol + 21.7 g of tert-butanol), Temp = 95 oC.

25. Recovery and Reusability Studies Reaction condition: Glycerol: tert-butanol=1:6, M-PDVB-8 Catalyst = 0.30g, Temp = 95 oC. Regeneration with 0.5 M Sulfuric acid washing

26. Summary and Conclusions • Sulfonic acid functionalized mesoporous polymer exhibited to be highly active catalyst for glycerol etherification. • M-PDVB-SO3H showed higher glycerol conversion compared to other porous catalysts screened, due to its large pore size and easy diffusivity of molecules. • M-PDVB-SO3H with different amount of acidic sites results in glycerol conversion from 65 to 82 % with h-GTBE selectivity of 34% at 6h. • M-PDVB-8 containing 1.9 mmol/g resulted in higher TON of 94 and it is selected for the further studies. • M-PDVB-8 showed higher h-GTBE selectivity of 44% with 86% glycerol conversion at 95oC with 1:6 mole ratio. • Reusability of the catalyst reveals a slight decrease in h-GTBE selectivity, but the glycerol conversion remains almost the same.

27. Acknowledgements: Funding Agencies Vision Group on Science & Technology, Government of Karnataka, India

29. Raw Materials • Rapeseed, the major source (>80%) • Sunflower oil (10%, Italy and Southern France) • Soybean oil (USA) • Palm oil (Malaysia) • Linseed, olive oils (Spain) • Cottonseed oil (Greece) • Beef tallow (Ireland), Jatropha (Nicaragua),