Abstract: Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.
Abstract: In industrial scale of Gas to Liquid (GTL) process in
Fischer-Tropsch (FT) synthesis, a part of reactor outlet gases such as
CO2 and CH4 as side reaction products, is usually recycled. In this
study, the influence of CO2 and CH4 on the performance and
selectivity of Co-Ru/Al2O3 catalyst is investigated by injection of
these gases (0-20 vol. % of feed) to the feed stream. The effect of
temperature and feed flow rate, are also inspected. The results show
that low amounts of CO2 in the feed stream, doesn`t change the
catalyst activity significantly but increasing the amount of CO2 (more
than 10 vol. %) cause the CO conversion to decrease and the
selectivity of heavy components to increase. Methane acts as an inert
gas and doesn`t affect the catalyst performance. Increasing feed flow
rate has negative effect on both CO conversion and heavy component
selectivity. By raising the temperature, CO conversion will increase
but there are more volatile components in the product. The effect of
CO2 on the catalyst deactivation is also investigated carefully and a
mechanism is suggested to explain the negative influence of CO2 on
catalyst deactivation.
Abstract: Performance of a cobalt doped sol-gel derived silica (Co/SiO2) catalyst for Fischer–Tropsch synthesis (FTS) in slurryphase reactor was studied using paraffin wax as initial liquid media. The reactive mixed gas, hydrogen (H2) and carbon monoxide (CO) in a molar ratio of 2:1, was flowed at 50 ml/min. Braunauer-Emmett- Teller (BET) surface area and X-ray diffraction (XRD) techniques were employed to characterize both the specific surface area and crystallinity of the catalyst, respectively. The reduction behavior of Co/SiO2 catalyst was investigated using the Temperature Programmmed Reduction (TPR) method. Operating temperatures were varied from 493 to 533K to find the optimum conditions to maximize liquid fuels production, gasoline and diesel.