EFFECT OF Au LOADING OVER ACTIVATED CARBON SUPPORT FOR VINYL CHLORIDE MONOMER PRODUCTION VIA ACETYLENE

HYDROCHLORINATION

1Center of Excellence on Catalysis and Catalytic Reaction Engineering Department of Chemical EngineeringFaculty of Engineering, Chulalongkorn University, THAILAND

2The Joint Graduate School of Energy and Environment, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand

3Thai Plastic And Chemicals Public CO., LTD., Maptaput Industrial Estate,Muang District, Rayong 21150, Thailand

Boonvara Ngamlertkul1, Wiboon Wittanadecha1, Navadol Laosiripojana2, Piyasan Praserthdam1, Anawat Ketcong3,

Suttichai Assabumrungrat*,1

Content

Conclusion and Acknowledgements

Introduction

Objective and Theory

Material and Method

Results and discussion

Introduction

Vinyl chloride monomer(VCM)

Polymerization

Poly vinyl chloride (PVC)

PVC is the third of most production plasticPVC is the third of most production plastic

PVC product

Pipe ValveValve WireWire FrameFrame

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

In ChinaFor over 100$ for long period, the calcium carbide method exhibits obvious price advantage

For over 100$ for long period, the calcium carbide method exhibits obvious price advantage

C2H4 + Cl2 CH2ClCH2Cl ; ΔH = -171.7 kj·mol-1

CH2ClCH2Cl CH2CHCl + HCl

C2H4 + 2HCl + 1/2O2 CH2ClCH2Cl + H2O ;

ΔH = -251 kj·mol-1

FeCl3

450-550°C

220-300°CCuCl2

CaO + 3C CaC2 + CO

CaC2 + 2H2O C2H2 + Ca(OH)2

2NaCl + 2H2O 2NaOH + 2HCl

C2H2 + HCl CH2CHCl ; ΔH = -124.8 kj·mol-1

High Temp.

Electrolysis

HgCl2

Petroleum

based

Carbide

based

170-180°C

Kai zhuo et al., Fuel processing Technology. 2012 HgCl2 loss

WE NEEDNON-MERCURY

CATALYST!!

Volatile of mercury compound during reaction.

Mercury catalyst is the major source of environmental issues.

Major problem of acetylene hydrochlorination process

Why we select Au catalyst?

Hutching G et al., Journal of Catalysis. 1985Hutching G, Catalysis Today. 2005

Au3+, E0 = 1.42V which have been shown to be greatly active and selective

Reaction mechanism

Shengjie Wang et al., Catalysis Letters. 2010

MCln·C2H2 + HCl MCln·C2H3Cl

MCln·C2H3Cl MCln + C2H3Cl

HCl reacts with the C2H2 complex

C2H3Cl desorbs from the surface of catalyst

MCln + C2H2 MCln·C2H2

C2H2 reacts with the catalyst site

Deactivation of Au catalyst

0 50 100 150 2000

1

2

3

4

5

6

Temperature/°C

Dea

ctiv

atio

n r

ate

Deactivation from coke deposition

Deactivation from Reduction from Au3+ to Au0

B. Nkosi et al., Journal of Catalysis. 1991

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

Material and method

HAuCl3+Aqua regia

Impregnation Dried at110°C, 24 hr

Characterization

XRD technique is able to identify Au0 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.

Material and method

Acetylene

Hydrogen Chloride

Nitrogen

Reg 1

Reg 2

F

FIC-1

F

FIC-2

F

FIC-3

NaOH

GC

VentReg 3

Heating at 120°C, 30 min for eliminate water

Material and method

Acetylene

Hydrogen Chloride

Nitrogen

Reg 1

Reg 2

F

FIC-1

F

FIC-2

F

FIC-3

NaOH

GC

VentReg 3

Regenerate catalyst at 160°C, 60 min

Material and method

Acetylene

Hydrogen Chloride

Nitrogen

Reg 1

Reg 2

F

FIC-1

F

FIC-2

F

FIC-3

NaOH

GC

VentReg 3

180°C

Result and discussion

0 1 2 30

10

20

30

40

50

60

70

80

0.3wt%Au

0.5wt%Au

1.0wt%Au

1.5wt%Au

2.0wt%Au

Time(hr)

Ace

tyle

ne

con

vers

ion

(%

)

Result and discussion

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 20

10

20

30

40

50

60

70

80

90

Au loading amount (%wt)

Ace

tyle

ne

con

vers

ion

(%

)

0.00 0.50 1.00 1.50 2.00 2.50 3.000

10

20

30

40

50

60

70

80

90

Time(hr)

Ace

tyle

ne

con

vers

ion

(%

) 1wt% Au

HgCl2

1%wt Au shows higher performance than HgCl2

Commercial catalyst

Result and discussion

Result and discussion

At 1.5wt% and 2wt% after run found Au0 peak

Au0

Activated carbon

After reaction

Before reaction

Conclusion1

2

The optimum of Au loading was 1wt%Au.

The results indicate that the state of Au was changed from Au3+ to Au0 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.

Conclusion

3Gold (III) chloride catalyst shows higher catalytic activity than the commercial catalyst (HgCl2) because of the higher standard electrode potential.

Acknowledgements

This work was supported by Thai Plastic and

Chemicals Public Company Limited (TPC).

Thank you for your attention

• Electron affinity is based on one electron processMn+ + e- M(n-1)+

• Interaction between C2H2 and metal chloride can be occurred the transfer of more than one electron, so standard electrode potential is more suitable for correlate with catalytic activityMn+ + ne- M

Hutching G et al., Journal of Catalysis. 1985

CC

∫+

∫-

Li Qianget al., Journal of petrochemical university, 2010

Comparation cost