03po XD 3 5 PDF
03po XD 3 5 PDF
03po XD 3 5 PDF
Shikong Shen, Changchun Yu, Xiaoping Dai, Zhiyong Pan, Qiying Jiang and Zhaobin Zhang The Key Laboratory of Catalysis CNPC University of Petroleum, Beijing 102200
1. Introduction During the last decade, interest in the conversion of natural gas to liquid hydrocarbons (GTL) by Fischer-Tropsch synthesis has grown significantly. Further improvement in GTL technology is still needed to strengthen its economic competitiveness. In the present work, a novel GTL technology suitable for smaller gas fields in remote areas is developed. This technology includes three steps: a) b) c) A two-stage oxidation process for syngas production A Fischer-Tropsch synthesis process without recycle of the F-T tail gas Utilization of the F-T tail gas of low heating value
A La2O3 promoted 7 wt% Ni/MgAl2O4-Al2O3 catalyst prepared according to [2], which has excellent activity for the partial oxidation of methane and methane reforming with CO2 and H2O to syngas, is used in the second reactor. In the catalyst preparation process, the support, Al2O3, reacts with MgO at the high temperature and forms a MgAl2O4 spinel compound on the surface of Al2O3. This hinders the formation of NiAl2O4 under POM reaction conditions and favors the dispersion of Ni on the catalyst surface. NiAl2O4 spinel is known to be inactive for the partial oxidation of methane, and is very difficult to reduce to active metal Ni. The function of the La promoter has been investigated using an isotopic switch method. This shows that the addition of La decreases the activity of Ni-based catalysts for CH4 decomposition and CO disproportionation, and leads to less carbon deposition from these reactions; thus La2O3promoted Ni/Al2O3 exhibits resistance to carbon deposition. Since a partial oxidation with air to produce synthesis gas can reduce capital and production costs of GTL for smaller scale F-T process without a recycle loop [3], air was used as the oxygen resource in these experiments. The experimental data from reaction conditions in range of 973~1323 K (in second reactor), 0.1~2 MPa and GHSV=10,000~30,000 h-1 are quite close to the thermodynamic equilibrium. A 300 h on stream run at 1173 K and 2 MPa shows that both catalysts exhibit good activity and stability.
5. Conclusion
A smaller scale GTL using a two-stage methane oxidation with air to produce syngas in combination with a F-T synthesis process without a recycle loop can reduce capital and production costs. This GTL technology is suitable for smaller gas fields in remote areas. Preliminary economic assessment shows that the GTL liquid product cost is ~US$20/bbl at a gas price of US$0.50/MMBTU.
Acknowledgements
This work is supported by the PetroChina Company Limited and Major State Basic Research Projects of the Ministry of Science and Technology of China (G1999022402). The authors gratefully acknowledge the support of K. C. Wong Education Foundation, Hong Kong.
References
[1] Eisenberg, B., Fiato R. A., Kaufman, T. G., Bauman, R. F., Chemtech , Oct.1999, 32. [2] Zhang, C., Yu, C., Shen, S., CUIHUA XUEBAO (Chinese J. Catal.), 2000,21(1),14. [3] Rhodes, A. K., Oil & Gas Journal, Dec. 30, 1996, 85.