1. EFFECT OF Au LOADING OVER ACTIVATED CARBON SUPPORT FOR VINYL CHLORIDE MONOMER PRODUCTION VIA ACETYLENE HYDROCHLORINATION 1 Center of Excellence on Catalysis and Catalytic Reaction Engineering Department of Chemical Engineering Faculty of Engineering, Chulalongkorn University, THAILAND 2 The Joint Graduate School of Energy and Environment, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand 3 Thai Plastic And Chemicals Public CO., LTD., Maptaput Industrial Estate, Muang District, Rayong 21150, Thailand Boonvara Ngamlertkul 1, Wiboon Wittanadecha 1, Navadol Laosiripojana 2, Piyasan Praserthdam 1, Anawat Ketcong 3, Suttichai Assabumrungrat *,1

2. Content Conclusion and Acknowledgements Introduction Objective and Theory Material and Method Results and discussion

3. Introduction Vinyl chloride monomer (VCM) Polymerization Poly vinyl chloride (PVC)

4. PVC is the third of most production plastic PVC product Pipe Valve Wire Frame

5. 2006 2007 2008 2009 2010 10.59 million tons 12.72 million tons 15.81 million tons 17.81 million tons 20.43 million tons Kai zhuo et al., Fuel processing Technology. 2012 PVC production in China

6. In China For over 100$ for long period, the calcium carbide method exhibits obvious price advantage C 2 H 4 + Cl 2 CH 2 ClCH 2 Cl ; ΔH = -171.7 kj·mol -1 CH 2 ClCH 2 ClCH 2 CHCl + HCl C 2 H 4 + 2HCl + 1/2O 2 CH 2 ClCH 2 Cl + H 2 O ; ΔH = -251 kj·mol -1 FeCl 3 450-550°C 220-300°C CuCl 2 CaO + 3CCaC 2 + CO CaC 2 + 2H 2 OC 2 H 2 + Ca(OH) 2 2NaCl + 2H 2 O2NaOH + 2HCl C 2 H 2 + HCl CH 2 CHCl ; ΔH = -124.8 kj·mol -1 High Temp. Electrolysis HgCl 2 Petroleum based Carbide based 170-180°C Kai zhuo et al., Fuel processing Technology. 2012 HgCl 2 loss

7. Volatile of mercury compound during reaction. Mercury catalyst is the major source of environmental issues.

8. Why we select Au catalyst? Hutching G et al., Journal of Catalysis. 1985 Hutching G, Catalysis Today. 2005 Au 3+, E 0 = 1.42V which have been shown to be greatly active and selective

9. Reaction mechanism Shengjie Wang et al., Catalysis Letters. 2010 MCl n ·C 2 H 2 + HClMCl n ·C 2 H 3 Cl MCl n ·C 2 H 3 ClMCl n + C 2 H 3 Cl HCl reacts with the C 2 H 2 complex C 2 H 3 Cl desorbs from the surface of catalyst MCl n + C 2 H 2 MCl n ·C 2 H 2 C 2 H 2 reacts with the catalyst site

10. Deactivation of Au catalyst Deactivation from coke deposition Deactivation from Reduction from Au 3+ to Au 0 B. Nkosi et al., Journal of Catalysis. 1991

11. Material and method Commercial activated carbon 100 mesh Dipping into HCl 1M Heating at 70°C, 6 hr Washing by DI, Adjust pH = 7 Dried at 110°C, 24 hr Activated carbon support

12. Material and method HAuCl 3 +Aqua regia Impregnation Dried at 110°C, 24 hr

13. Characterization XRD technique is able to identify Au 0 which indicates the deactivation of catalyst. It should be noted that other techniques such as BET, XPS and TGA were not employed for catalyst characterization as a corrosive gas could be generated during characterization and become harmful to the equipments.

14. Material and method Heating at 120°C, 30 min for eliminate water

15. Material and method Regenerate catalyst at 160°C, 60 min

16. Material and method 180°C

17. Result and discussion

19. 1wt% Au HgCl 2 1%wt Au shows higher performance than HgCl 2 Commercial catalyst Result and discussion

20. At 1.5wt% and 2wt% after run found Au 0 peak Au 0 Activated carbon After reaction Before reaction

21. Conclusion 1 2 The optimum of Au loading was 1wt%Au. The results indicate that the state of Au was changed from Au 3+ to Au 0 during the reaction for the high Au loading. This might be a reason for the insignificant improvement of acetylene conversion at Au loading of 1.5 and 2wt%. It should be noted that another possibility may be from the poor Au dispersion at high Au loading.

22. Conclusion 3 Gold (III) chloride catalyst shows higher catalytic activity than the commercial catalyst (HgCl 2 ) because of the higher standard electrode potential.

23. Acknowledgements This work was supported by Thai Plastic and Chemicals Public Company Limited (TPC).

24. Thank you for your attention

27. Electron affinity is based on one electron process  M n+ + e - M (n-1)+ Interaction between C 2 H 2 and metal chloride can be occurred the transfer of more than one electron, so standard electrode potential is more suitable for correlate with catalytic activity  M n+ + ne - M Hutching G et al., Journal of Catalysis. 1985

28. C C ∫+∫+ ∫-∫-

29. Li Qianget al., Journal of petrochemical university, 2010

30. Comparation cost