Fischer-Tropsch Technology Using a Two-stage Reactor for the Catalytic Oxidation of Methane to Synthesis Gas

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

2. Two-stage oxidation process for syngas production

Most research and development work has focused on the syngas production step which accounts for more than 60% of the total investment in conventional GTL processes. Reducing the cost of syngas production will greatly improve the overall economics of the GTL process. Catalytic partial oxidation of methane (CPOM) to syngas is a slightly exothermic, highly selective, and energy efficient process. It gives syngas with a hydrogen to carbon monoxide ratio of 2:1 that is suitable for F-T synthesis. However, a CPOM process has not yet been commercialized. Major engineering problems still exist which are the high temperature gradient and the risk of explosion because the premixed CH4/O2 mixtures are within the ignition and explosion limits. In a fluidized bed reactor the heat transfer is much better owing to the back mixing, which ensures a uniform temperature and a safer operation. A technology for syngas production by contacting methane with limited amounts of steam and oxygen in a catalytic fluidized bed reactor has been developed by Exxon[1]. In the present work, an alternative approach for syngas production was investigated. This process consists of two consecutive fixed-bed reactors in which oxygen or air is introduced separately into the two reactors. In this way the ratio of methane to oxygen is above the ignition and explosion limits in each reactor. The first reactor, packed with a perovskite oxide catalyst, is used for the catalytic combustion of methane at a lower ignition temperature (<723 K), and the second reactor filled with a Ni-based catalyst is used for methane partial oxidation and reforming with CO2 and H2O to syngas. About 25% of the oxygen and the entire methane are mixed and preheated to 723 K in a waste heat recovery boiler that recovers the heat content of the effluent from second reactor. This mixture is then fed to the first reactor. In the first reactor, 6~7% of the methane is oxidized to CO2 and H2O and at same time the reactants are heated to the temperature required for methane partial oxidation and reforming (>1073 K). The remaining oxygen (ca.70~75 %) is introduced in between the two reactors. In the second reactor, the exothermic partial oxidation of methane and the endothermic reforming reactions of methane with CO2 and H2O take place together and there is approximate thermal balance. In this way an adiabatic and safer operation can be achieved using a two-stage reactor process for the catalytic oxidation of methane to synthesis gas. In addition, if air is used as the oxidant, NOX is not produced because of the lower reaction temperature. A La0.7Ca0.3Fe0.3Mn0.7O3 perovskite oxide catalyst was found to be suitable for the combustion of methane in first reactor. The perovskite oxide catalyst exhibits a lower ignition temperature, good selectivity for complete combustion, and is resistant to carbon deposition under lean oxygen (the ratios of CH4 to O2 are 8:1~6:1) conditions.

* Corresponding author. Fax: +86-10-69744849, E-mail: skshen@263.net

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.

3. Fischer-Tropsch synthesis process without recycle of the F-T tail gas

A cerium oxide promoted Co/SiO2 catalyst was developed, which gives 99% conversion of CO and 86% selectivity to liquid hydrocarbons in a fixed bed reactor at 220C, 20 MPa and GHSV=500h-1. Cerium oxide acting as a chemical promoter not only increases CO conversion and C5+ selectivity, but also inhibits carbon deposition. A1000 hours stability test in a fixed bed reactor at 488 K, 1.5 MPa , GHSV 500 hr-1 and feed gas of H2/CO=2 shows that the cerium oxide promoted Co/SiO2 catalyst has good activity and stability. The average result of a total of 1000 hours is CO conversion of 90% and C5+ selectivity of 81%. The product distribution is liquid hydrocarbons in the range of C5-C10, C11-C20 and C20+ are 6.8%, 62.9 wt.% and 30.3 wt.% respectively. The chain growth probability of the catalyst is 0.9 calculated from the liquid hydrocarbon distribution according to Anderson-Schultz-Flory equation. The characterization of used catalysts by XRD, XPS and BET surface area prove that the catalyst has good chemical and structural stabilities. During the 1000 hours run, a slight decrease in catalytic activity can be accounted for by the covering of the catalyst surface and blocking of the catalyst pores by wax formed in the reaction. The activity can be regenerated easily by a hydrogen sweep at 673 K for 24 hour. The stability test demonstrates that the cerium oxide promoted Co/SiO2 catalyst is suitable for the Fischer-Tropsch synthesis process without a recycle of the F-T tail gas, because the high CO conversion and C5+ selectivity can reduce any loss due to unreacted CO and gaseous products.

4. Utilization of the F-T tail gas of low heat value

In the present process of methane oxidation with air to produce syngas and a F-T synthesis process without a recycle loop, the F-T tail gas contains methane 5.7 , CO 3.5 %, C2 0.4 % , C3 0.5 %, C4 0.4 %, CO2 0.7 % and a larger amount of nitrogen. A catalytic combustion technology was developed for utilizing the F-T tail gas of low heat value to generate heat energy or power.

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.