Attrition Resistant Iron-Based Catalysts For F-T SBCRs

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+ H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-(FE) based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment; makes the separation of catalyst from the oil/wax product very difficult, if not impossible; and results in a steady loss of catalyst from the reactor. Under a previous Department of Energy (DOE)/University Research Grant (UCR) grant, Hampton University reported, for the first time, the development of demonstrably attrition-resistant Fe F-T synthesis catalysts having good activity, selectivity, and attrition resistance. These catalysts were prepared by spray drying Fe catalysts with potassium (K), copper (Cu), and silica (SiO{sub 2}) as promoters. SiO{sub 2} was also used as a binder for spray drying. These catalysts were tested for activity and selectivity in a laboratory-scale fixed-bed reactor. Fundamental understanding of attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried HPR-43 catalyst having average particle size (aps) of 70 {micro}m with high attrition resistance. This HPR-43 attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5+} selectivity of >78% and methane selectivity of less than 5% at an {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University of Kentucky. Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5+} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2})

Development of Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away from fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of Fe FT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. The results show that use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO{sub 2} wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5}{sup +} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2})

Carbon Dioxide Separation by Phase Enhanced Gas-Liquid Absorption Annual Report

A new process called phase enhanced gas-liquid absorption has been developed in its early stage. It was found that adding another phase into the absorption system of gas/aqueous phase could enhance the absorption rate. A system with three phases was studied. In the system, gas phase was carbon dioxide. Two liquid phases were used. One was organic phase. Another was aqueous phase. By addition of organic phase into the absorption system of CO{sub 2}-aqueous phase, the absorption rate of CO{sub 2} was increased significantly. CO{sub 2} finally accumulated into aqueous phase. The experimental results proved that (1) Absorption rate of carbon dioxide was enhanced by adding organic phase into gas aqueous phase system; (2) Organic phase played the role of transportation of gas solute (CO{sub 2}). Carbon dioxide finally accumulated into aqueous phase