348
in the order: Ni/Al 2 O 3 > Ni/SBA-15 > Ni/ZrO 2 > Ni/CeO 2 -ZrO 2 > Ni/TiO 2 > Ni/
MgO, the stability and the coking resistance of SBA-15 and ZrO 2 catalyst was the
highest [48]. High coking resistance of Ni/ZrO 2 catalyst has also been observed by
Singha et al. [49] and Lino et al. [50]. Similarly, it was found that a NiO–YSZ–CeO 2
catalyst had better stability than commercial Holder Topsoe and Imperial Chemical
Industries catalysts [51]. On the other hand, Pino et al. observed activity enhancement on Ni/CeO 2 catalyst which was doped with La [52]. Further, Majewski et al.
[53] studied the effect on O 2 and H 2 O over Ni/SiO 2 catalyst and found that while
oxygen increases methane conversion and reduces coke deposition in agreement
with our study, water reduces H 2 /CO ratio, in contrast to equilibrium predictions.
Furthermore, Garcia-Vargas et al. [54] compared the CeO 2 support with β-SiC for
Ni-based catalyst and observed that lower H 2 /CO ratio for ceria support was due to
more basic sites in a ceria-supported catalyst. Thus, in addition to the feed composition and operating conditions, catalyst design plays an important role in achieving
higher methane conversion and H 2 /CO ratio, while having less carbon deposition on
the catalyst, for the tri-reforming reaction.
7 Conclusion
It has been observed that adding oxygen to DRM reaction reduces carbon deposition and does not affect methane conversion significantly. Although theoretically, O 2
reduces H 2 /CO ratio, our experimental results show a marginal increase in this ratio
due to O 2 . Nevertheless, H 2 /CO ratio is not sufficient and warrants further addition
of water to the reaction mixture. Thus, in principle flue gas can be used to reform
methane. However, in order to achieve net CO 2 consumption further improvement
of tri-reforming process is required. In this direction, we modelled the tri-reforming
using flue gas as the feed. In the model, we implemented CO 2 separation and recycle
to the reactor, achieving an H 2 /CO ratio in the syngas that can be used for the
production of petrochemicals while attaining a net CO 2 fixation. Thus, components
of flue gas help improve properties of syngas and with an innovative process design,
and a net CO 2 consumption can be attained.
References
1. Song CS, Wei P (2004) Tri-reforming of methane: a novel concept for catalytic production of
industrially useful synthesis gas with desired H2/CO ratios. Catal Today 98:463–484
2. IEA (2020), India 2020, IEA, Paris https://www.iea.org/reports/india-2020
3. Jacob A, Moulijn MM (2001) Annelies Van Diepen. Wiley, Chemical Process Technology
4. Wei JM, Iglesia E (2004) Isotopic and kinetic assessment of the mechanism of reactions of CH 4
with CO 2 or H 2 O to form synthesis gas and carbon on nickel catalysts. J Catal 224:370–383
5. Chein RY, Chen YC, Yu CT, Chung JN (2015) Thermodynamic analysis of dry reforming of
CH 4 with CO 2 at high pressures. J Nat Gas Sci Eng 26:617–629
S. Gupta et al.
in the order: Ni/Al 2 O 3 > Ni/SBA-15 > Ni/ZrO 2 > Ni/CeO 2 -ZrO 2 > Ni/TiO 2 > Ni/
MgO, the stability and the coking resistance of SBA-15 and ZrO 2 catalyst was the
highest [48]. High coking resistance of Ni/ZrO 2 catalyst has also been observed by
Singha et al. [49] and Lino et al. [50]. Similarly, it was found that a NiO–YSZ–CeO 2
catalyst had better stability than commercial Holder Topsoe and Imperial Chemical
Industries catalysts [51]. On the other hand, Pino et al. observed activity enhancement on Ni/CeO 2 catalyst which was doped with La [52]. Further, Majewski et al.
[53] studied the effect on O 2 and H 2 O over Ni/SiO 2 catalyst and found that while
oxygen increases methane conversion and reduces coke deposition in agreement
with our study, water reduces H 2 /CO ratio, in contrast to equilibrium predictions.
Furthermore, Garcia-Vargas et al. [54] compared the CeO 2 support with β-SiC for
Ni-based catalyst and observed that lower H 2 /CO ratio for ceria support was due to
more basic sites in a ceria-supported catalyst. Thus, in addition to the feed composition and operating conditions, catalyst design plays an important role in achieving
higher methane conversion and H 2 /CO ratio, while having less carbon deposition on
the catalyst, for the tri-reforming reaction.
7 Conclusion
It has been observed that adding oxygen to DRM reaction reduces carbon deposition and does not affect methane conversion significantly. Although theoretically, O 2
reduces H 2 /CO ratio, our experimental results show a marginal increase in this ratio
due to O 2 . Nevertheless, H 2 /CO ratio is not sufficient and warrants further addition
of water to the reaction mixture. Thus, in principle flue gas can be used to reform
methane. However, in order to achieve net CO 2 consumption further improvement
of tri-reforming process is required. In this direction, we modelled the tri-reforming
using flue gas as the feed. In the model, we implemented CO 2 separation and recycle
to the reactor, achieving an H 2 /CO ratio in the syngas that can be used for the
production of petrochemicals while attaining a net CO 2 fixation. Thus, components
of flue gas help improve properties of syngas and with an innovative process design,
and a net CO 2 consumption can be attained.
References
1. Song CS, Wei P (2004) Tri-reforming of methane: a novel concept for catalytic production of
industrially useful synthesis gas with desired H2/CO ratios. Catal Today 98:463–484
2. IEA (2020), India 2020, IEA, Paris https://www.iea.org/reports/india-2020
3. Jacob A, Moulijn MM (2001) Annelies Van Diepen. Wiley, Chemical Process Technology
4. Wei JM, Iglesia E (2004) Isotopic and kinetic assessment of the mechanism of reactions of CH 4
with CO 2 or H 2 O to form synthesis gas and carbon on nickel catalysts. J Catal 224:370–383
5. Chein RY, Chen YC, Yu CT, Chung JN (2015) Thermodynamic analysis of dry reforming of
CH 4 with CO 2 at high pressures. J Nat Gas Sci Eng 26:617–629
S. Gupta et al.