An active iron catalyst containing sulfur for Fischer–Tropsch synthesis

Abstract A precipitated iron catalyst containing sulfur for Fischer–Tropsch (F–T) synthesis was prepared by means of a novel method using a ferrous sulfate as precursor. Both fixed bed reactor (FBR) and continues stirred tank slurry reactor (STSR) were used to test long-term F–T reaction behaviors over the catalyst. A stability test (1600 h) in FBR showed that the catalyst was active even after 1500 h of time-on-stream with CO conversion of 78% and with C5+ hydrocarbon selectivity of 72 wt% at 250 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H2/CO=2.0. The test (550 h) in STSR indicated that the catalyst exhibited relatively high activity with CO conversion of 70–76% and C5+ selectivity of 83–86 wt% in hydrocarbon products under the conditions of 260 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H2/CO=0.67. The deactivation rate of the catalyst was low, accompanied by surprisingly low methane selectivity of 2.0–2.9 wt%. It is shown that a small amount of sulfur (existing as SO42−) may promote the catalyst by increasing activity and improving the heavier hydrocarbon selectivity. It is also comparable with other typical iron catalysts for F–T synthesis.

[1]  Diane Hildebrandt,et al.  The effect of sulfur on supported cobalt Fischer–Tropsch catalysts , 1999 .

[2]  D. Bukur,et al.  Binder/support effects on the activity and selectivity of iron catalysts in the Fischer-Tropsch synthesis , 1990 .

[3]  Hongwei Xiang,et al.  Slurry phase Fischer–Tropsch synthesis over manganese-promoted iron ultrafine particle catalyst , 2002 .

[4]  B. Davis,et al.  The effect of sulfate on the crystal structure of zirconia , 1991 .

[5]  M. F. Zarochak,et al.  Effect of initial was medium on the Fischer-Tropsch slurry reaction , 1997 .

[6]  A. Datye,et al.  The synthesis of attrition resistant slurry phase iron Fischer–Tropsch catalysts , 2000 .

[7]  D. Bukur,et al.  Activation studies with a promoted precipitated iron Fischer-Tropsch catalyst , 1989 .

[8]  A. Datye,et al.  Attrition of precipitated iron Fischer-Tropsch catalysts , 1995 .

[9]  B. Jager,et al.  Advances in low temperature Fischer-Tropsch synthesis , 1995 .

[10]  Johan Andries Kritzinger,et al.  The role of sulfur in commercial iron-based Fischer-Tropsch catalysis with focus on C2-product selectivity and yield , 2002 .

[11]  Santosh K. Gangwal,et al.  Development of Fe Fischer–Tropsch catalysts for slurry bubble column reactors , 2000 .

[12]  Snehal A. Patel,et al.  Fixed bed and slurry reactor studies of Fischer-Tropsch synthesis on precipitated iron catalyst , 1990 .

[13]  Snehal A. Patel,et al.  Promoter effects on precipitated iron catalysts for Fischer-Tropsch synthesis , 1990 .

[14]  R. E. Kelly,et al.  Fischer--Tropsch synthesis. Some important variables of the synthesis on iron catalysts. [Increased activity obtained using Fe catalyst D-3001 containing MgO 6. 8, SiO/sub 2/, 1. 05, C/sub 2/O/sub 3/ 0. 96, and K/sub 2/O 0. 85% as promoters] , 1952 .

[15]  Hongwei Xiang,et al.  Effect of reaction conditions on the product distribution during Fischer–Tropsch synthesis over an industrial Fe-Mn catalyst , 2001 .

[16]  D. Bukur,et al.  Highly active and stable iron Fischer-Tropsch catalyst for synthesis gas conversion to liquid fuels , 1999 .

[17]  Yongqing Zhang,et al.  Fischer−Tropsch synthesis: activity and selectivity for Group I alkali promoted iron-based catalysts , 2002 .

[18]  D. Bukur,et al.  Activation studies with a precipitated iron catalyst for Fischer-Tropsch synthesis. I. Characterization studies , 1995 .

[19]  Abhaya K. Datye,et al.  Phase Transformations in Iron Fischer–Tropsch Catalysts during Temperature-Programmed Reduction , 2000 .

[20]  S. Reyes,et al.  Primary and secondary reaction pathways in ruthenium-catalyzed hydrocarbon synthesis , 1991 .

[21]  C. Satterfield,et al.  EVIDENCE FOR TWO CHAIN GROWTH PROBABILITIES ON IRON CATALYSTS IN THE FISCHER‐TROPSCH SYNTHESIS , 1984 .

[22]  Lech Nowicki,et al.  Activation studies with a precipitated iron catalyst for Fischer-Tropsch synthesis. II. Reaction studies , 1995 .

[23]  N. Coville,et al.  The effect of sulfide ions on a precipitated iron Fischer–Tropsch catalyst , 1999 .

[24]  Santosh K. Gangwal,et al.  Spray-Dried Iron Fischer−Tropsch Catalysts. 1. Effect of Structure on the Attrition Resistance of the Catalysts in the Calcined State , 2001 .

[25]  D. Bukur,et al.  Fischer-tropsch synthesis in a stirred tank slurry reactor , 1994 .

[26]  J. Niemantsverdriet,et al.  Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the fischer tropsch reaction , 1982 .

[27]  A. Chaffee,et al.  Sulfur Poisoning of Fischer-Tropsch Synthesis Catalysts in a Fixed-Bed Reactor , 1989 .

[28]  Abhaya K. Datye,et al.  Activation of Precipitated Iron Fischer-Tropsch Synthesis Catalysts , 1995 .

[29]  Calvin H. Bartholomew,et al.  Sulfur poisoning of cobalt and iron fischer-tropsch catalysts , 1985 .