1. Conversion of Poly(Vinyl Chloride) to Fuel Oil Using NiMo Catalyst on Silica Alumina and Acid Catalyst NiMo Catalyst on Silica Alumina and Acid Catalyst Dr. Chanatip Samart Dr. Chanatip Samart Department of Chemistry, Thammasat University Assoc. Prof. Apinya Duangchan Department of Chemical Engineering, Kasetsart University ประชุมวิชาการ วิจัยพลังงาน สร้างฐานเศรษฐกิจพอเพียง กรุงเทพฯ 13-14 ธันวาคม 2549

2. Introduction Table1 Percentage composition of simulated plastic waste.

3. Recycling Technology  Primary Recycling  Secondary Recycling  Tertiary Recycling  Quaternary Recycling

4. Tertiary Recycling  Thermal Cracking  Catalytic Cracking  Hydrocracking

5. Polyvinyl chloride (PVC) Fig 1 Structure of polyvinyl chloride - High mechanical strength - High polar - Non flamable

6. Polypropylene (PP) Fig 2 Structure of polypropylene - Isotactic - Syndiotactic - Atactic

7. Experimental

8. Pyrolysis process diagram Carrier gas, N 2 Plastics Tube reactor Cooling water Liquid product Gas product Absorber

9. Product analysis - Gas product Analyzed C1-C3 by gas chromatograph porapak q column equipped with FID detector - liquid product Fractionation by distillation in 4 boiling temperature range IBP-200 0 C 201-250 0 C 251-370 0 C >370 0 C

10. Analysis of gasoline (IBP-200 0 C) product - Determination of Benzene Toluene and Xylene (BTX) Gas chromatograph OV101 column equipped with FID detector - Determination of Octane Number by NMR

11. Octane number of gasoline fraction by NMR A B CD E F

12. Aromatics, vol % = [(A+C/3) 0.97  102] / [(A+C/3)0.97+ 2B+E/2+F/3)1.02+3.33B] Paraffins, vol% = [(D-2B+E/2+F/3)1.02  102] / [(A+C/3)0.97+(D- 2B+E/2+F/3)1.02 +3.33B] Olefins, vol% = [3.33B  102] / [(A+C/3)0.97+(D- 2B+E/2+F/3)1.02+3.33B] isoparaffin index (CH3:CH2)= 2F:3E RON = 80.2 + 8.9 (isoparaffin index) + 0.107 (aromatics) MON = 70.8 + 10 (isoparaffin index) + 0.101 (aromatics)

13. Result and Discussion

14. Study the decomposition of PVC by TGA

15. The yields of product at various pyrolysis temperature and carrier gas Oil and Gas Temperature increase to 500 0 C Solid At 600 0 CGasSolid Hydrogen Gas Oil

16. The gas composition at various pyrolysis temperature and carrier gas Pyrolysis temperature increase Methane yield

17. Fraction of liquid products derived from pyrolysis of PVC Pyrolysis temperature increase Gasoline yield

18. BTX content of pyrolysed PVC at various temperatures Temperature BTX content Hydropyrolysis < PyrolysisBTX content

19. Synergistic effect of PP:PVC for pyrolysis (oil:gas:solid = 65%:35%:0% for PP and 6.5%:71.3%:22.2% for PVC)

20. The gas composition at various ratio of PP:PVC At ratio 2:1 and 3:1 give high ethane yield.

21. Fraction of liquid product derived from different ratios of PP: PVC at 450 0 C

22. BTX Content in oil from pyrolysis of mixed PP and PVC

23. The yields of product at various type of catalyst at PP:PVC =1:1

24. The gas composition at various type of catalyst at PP:PVC = 1:1

25. Fraction of liquid product derived from different type of catalyst at PP:PVC=1:1

26. BTX Content in oil from pyrolysis various type of catalyst at PP:PVC=1:1

27. Determination of octane number Sam ple PP:PVCType of catalyst % cataly st Temp

28. Sample %aromatic %paraffin %olefin H:C isoparafin index RON MON Octane number and hydrocarbon content - Low aromatic 2.8-4.3% - high octane number 120-170

29. Conclusions

30. Study pyrolysis of PVC When the temperature increases, oil yield increases - When the temperature increases, oil yield increases and solid decreases. and solid decreases. - At 600 0 C solid increases due to polymerization reaction. - Hydrogen decrease the pyrolysis activity - At high temperature 600 0 C methane is selective in hydrocarbon gas hydrocarbon gas - Gasoline decreased but gas oil and residue increase when temperature was increased due to polymerization reaction.

31. - Benzene Toluene and Xylene (BTX) increased when temperature was increased - BTX decreased when hydrogen was carrier gas due to BTX was hydrogenated.

32. Study pyrolysis of PVC mix PP - All of ratio have synergistic effect. - Ratio of PP:PVC 2:1 and 3:1 showed high yield of hydrocarbon gas. - Ethane was selective in hydrocarbon gas. - Gasoline and residue yield was high when PP ratio increased. - BTX decreased at high PP ratio because alkylation reaction generated to isoparaffin.

33. Study effect of catalyst - NiMo/Al2O3 catalyzed hydrogenation dehydrogenation reaction. - Silica alumina catalyzed cracking reaction - NiMo/SiO2Al2O3 was bifunctional catalyst and catalyzed dehydrocyclization.

34. Acknowledgements - Department of Chemistry, Kasetsart University - Department of Chemistry, King Mongkut Institute of Technology Ladkrabang - Ministry of Energy (EPPO) - Department of Chemical Engineering, Kasetsart University - The university staff development project of commission on higher education scholarship