effect of au loading over activated carbon support for vinyl chloride monomer production via...
TRANSCRIPT
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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
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Content
Conclusion and Acknowledgements
Introduction
Objective and Theory
Material and Method
Results and discussion
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Introduction
Vinyl chloride monomer(VCM)
Polymerization
Poly vinyl chloride (PVC)
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PVC is the third of most production plasticPVC is the third of most production plastic
PVC product
Pipe ValveValve WireWire FrameFrame
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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
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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
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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
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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
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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
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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
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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
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Material and method
HAuCl3+Aqua regia
Impregnation Dried at110°C, 24 hr
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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.
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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
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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
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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
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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
(%
)
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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
(%
)
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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
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Result and discussion
At 1.5wt% and 2wt% after run found Au0 peak
Au0
Activated carbon
After reaction
Before reaction
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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.
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Conclusion
3Gold (III) chloride catalyst shows higher catalytic activity than the commercial catalyst (HgCl2) because of the higher standard electrode potential.
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Acknowledgements
This work was supported by Thai Plastic and
Chemicals Public Company Limited (TPC).
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Thank you for your attention
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• 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
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CC
∫+
∫-
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Li Qianget al., Journal of petrochemical university, 2010
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Comparation cost