Investigation on Reverse Water-gas Shift over La2NiO4

Catalyst by cw-Cavity Enhanced Absorption

Spectroscopy during CH4/CO2 Reforming

B.S. Liu, Ling Li, C.T. Au1, A.S.-C. Cheung

Department of Chemistry, The University of Hong Kong, Pokfulam Road,
Hong Kong, China

1Departmentof Chemistry and Centre for Surface Analysis and Research, Hong
Kong Baptist University, Kowloon Tong, Hong Kong, China

Supported by the Research Grants Council of the Hong Kong Special

Administrative Region, China (Project No. HKU 7101/02P).
Background
Methane is available in huge quantity, besides burning,
there are many way to utilize it .

catalyst
CO2 reforming :
CH4 + CO2 2CO +2H2 Synthesis gas

Steam reforming:
CH4 + H2O CO + 3H2 Synthesis gas

Coupling reaction:
CH4 + CH4 C2H6 + etc
Aromatization:
nCH4 C6H6 , C10H8 +
Background
Numerous studies on CH4/CO2 reforming reaction using
Ni-based catalysts.
cat.
CH4 + CO2 2CO +2H2 Synthesis gas

Problems: (i) Low yield ( ~55%)

(ii) Carbon deposit (~after 1 hour)
Our studies:
Reverse water-gas shift (RWGS) reaction over La2NiO4
catalyst during CH4/CO2 reforming by continuous wave
cavity enhanced absorption spectroscopy (CEAS).
Associated
reaction:
CO2 + H2 CO + H2O
Experimental Setup for CEAS
Experimental Conditions:
Catalyst:

Ni(NO3)2 6 H2O + HNO3 + La2O3 La2NiO4 +

50 mg La2NiO4 sol-gel-generated catalyst at >500 oC

Laser system:

Tunable diode laser: 1279-1341 nm, 5 mW

Linewidth: 5 MHz

High reflective mirror: R > 0.99995

 Results
CEA spectra of CH4 and H2O obtained at different pulsing rate (of
CH4/CO2 reaction. (Temperature = 700 oC)

r
n
r= H2 O
n
n= CH4
n
n
n
2000 ms

1500 ms

1000 ms

500 ms

7510.5 7510.8 7511.1 7511.4

-1
Wavenumber (cm )
HITRAN Data Base
Vibrational
Molecule Absorption (cm-1) transition Rotational

CH4 7510.59 7511.20 210 310 J =0 (Q

branch)

H2O 7511.30 110 310 J = 5, Ka = 0, Kc= 5

J = 6, Ka = 2, Kc= 4
 Results
CEA spectra of CH4 and H2O obtained at different pulsing rate (of
CH4/CO2 reaction. (Temperature = 700 oC)

r
n
r= H2 O
n
n= CH4
n
n
n
2000 ms

1500 ms

1000 ms

500 ms

7510.5 7510.8 7511.1 7511.4

-1
Wavenumber (cm )
CEA spectra of CH4 and H2O obtained at different time on stream.
(reaction temperature =700 oC); fixed pulsing duration

n CH4 r

r H2 O n
n
n 225 min
After long
95 min reaction time,
deactivation of
15 min catalyst

0 min

7510.6 7510.8 7511.0 7511.2 7511.4

-1
Wavenumber (cm )
Results
(1) The conversion of CO2 over La2NiO4 catalyst was
nearly 8.0 % higher than that of methane,
attributable to the contribution of RWGS reaction:

CO2 + H2 CO + H2O H = + 41 kJ/mol

(More than one channel for the consumption of CO2)

(2) The H2O formation in RWGS reaction increases as

the temperature of the catalyst increases because of
the formation of more H2.

CH4 + CO2 2CO + 2H2

High Resolution Transmission electron microscopy (HRTEM)
images of as-prepared La2NiO4 sol-gel-generated catalyst
HRTEM photographs of used La2NiO4 catalyst for CH4/CO2
reforming for 5 h under the condition of supersonic jet
expansion; scale (a) 200 nm (b) 5 nm.

(a) (b)
Conclusion and Future work

Cavity enhanced absorption spectroscopy(CEAS) is an

excellent technique for monitoring catalytic reaction in situ.

The reverse water-gas shift (RWGS) reaction promoted the

conversion of CO2 and decreased the partial pressure of
hydrogen.

With high sensitivity, it is envisaged that chemical

intermediates such as HCO, OH and CH3 radicals produced
in catalytic reaction could also be detected and studied.
Schematic Diagram of Cavity Ring-down / Raman Shifter Experimental Setup
Cavity ring down spectrum of CH4/CO2 reforming reaction at
different temperature (1573 nm).

CO2 CO CO2 o
700 C

o
600 C
Signal

o
500 C

o
400 C

CO2 CO2
room temp.

6357.0 6357.5 6358.0 6358.5 6359.0 6359.5

-1
Wavenumber /cm