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- Gavrilovic, Ljubisa, et al.
(författare)
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Deactivation of Co-based Fischer-Tropsch catalyst by aerosol deposition of potassium salts
- 2018
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Ingår i: Industrial & Engineering Chemistry Research. - Washington, USA : American Chemical Society (ACS). - 0888-5885 .- 1520-5045. ; 57:6, s. 1935-1942
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Tidskriftsartikel (refereegranskat)abstract
- A 20%Co/0.5%Re/γAl2O3 Fischer-Tropsch catalyst was poisoned by four potassium salts (KNO3, K2SO4, KCl, K2CO3) using the aerosol deposition technique, depositing up to 3500 ppm K as solid particles. Standard characterization techniques (H2 Chemisorption, BET, TPR) showed no difference between treated samples and their unpoisoned counterpart. The Fischer-Tropsch activity was investigated at industrially relevant conditions (210 °C, H2:CO = 2:1, 20 bar). The catalytic activity was significantly reduced for samples exposed to potassium, and the loss of activity was more severe with higher potassium loadings, regardless of the potassium salt used. A possible dual deactivation effect by potassium and the counter-ion (chloride, sulfate) is observed with the samples poisoned by KCl and K2SO4. The selectivity towards heavier hydrocarbons (C5+) was slightly increased with increasing potassium loading, while the CH4 selectivity was reduced for all the treated samples. The results support the idea that potassium is mobile under FT conditions. The loss of activity was described by simple deactivation models which imply a strong non-selective poisoning by the potassium species.
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| 5. |
- Gavrilovic, Ljubisa, et al.
(författare)
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Influence of potassium species on Co based Fischer-Tropsch-catalyst.
- 2016
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Konferensbidrag (refereegranskat)abstract
- 1. IntroductionThe purpose of this work is better understanding of the alkali influence on Co-based F-T catalyst. Since potassium is one of the elements that can be present in syngas from biomass[1], one of the questions is how potassium species affect the Co catalyst. From previous work it has been shown that alkali species act as poisons, thus deactivating catalysts[2]. Most previous work in this group[3][4] and by others[5] has concerned Co catalysts that were exposed to potassium species by incipient wetness impregnation, which is essentially different from the real behaviour during the gasification process where the species will mainly be in the vapor phase. In the present work we study potassium influence on a Co-based catalyst, using aerosol technology as a new method for potassium deposition on the Co surface. 2. Experimental4 different potassium salts were deposited using aerosol deposition on 20%Co/0.5%Re/γAl2O3. The amount of potassium salts deposited were determined using ICP analysis. Potassium salts were chosen from studies of the gases from biomass gasification[6]. These are K2SO4, KCl, KNO3 and K2CO3. KNO3 will be reduced to KOH during biomass gasification, but since in these experiments temperature was not so high and there was no H2/CO, most likely KNO3 will be deposited as such on the Co surface.BET N2 adsorption, H2 chemisorption, temperature programmed reduction (TPR) were used to characterize all the poisoned catalysts.Fischer Tropsch activity and selectivity measurements were performed at the in house build set-up, at 210°C, 20 bar and at H2:CO ratio of 2.1. The GHSV was consistently varied to maintain comparable CO conversion levels between 20-50%. A detailed description of the setup and procedures can be found elsewhere[3]. 3. ResultsThe potassium species were deposited using aerosol technology in the apparatus shown in Fig. 1. Potassium salts are dissolved in deionized water and the solution is placed inside the atomizer, which produces aerosol particles. Nitrogen is used as a carrier gas which forces aerosol particles in the reactor direction. Before entering the reactor, the gas mixture carrying the aerosol is passing the impaction vessel to remove large particles. The catalyst bed is placed in the middle of the reactor, which can be heated up to 800°C. The generated aerosol particles were physically characterized according to their electrical mobility using a scanning mobility particle sizer (SMPS) consisting of a differential mobility analyser (DMA) and a condensation particle counter (CPC)[7]. The three target concentrations of potassium salts, 200 ppm, 800 ppm and 4000 ppm, were monitored by the above-mentioned instruments.Results from characterization by elemental analysis, H2 chemisorption, BET surface area, TPR together with the results from the Fischer Tropsch synthesis i.e. CO conversion, selectivity, and activity will be compared with the same catalyst without any poison and also with previous results obtained from solution impregnation of the same poisons[8][3][9].4. DiscussionThe purpose of the work is to study how this procedure of poisoning Co catalyst with aerosol particles will affect catalyst performances during Fischer Tropsch reaction. Previous similar work on Ni catalyst in the SCR reaction using aerosol technology as a method of deposition, has proven loss in metallic surface area, decreasing of metal dispersion and severe reduction in the catalytic activity [7]. The idea is to develop a technique to transfer potassium species, and potentially other relevant impurities, in vapor phase to the catalyst surface. This new approach can to a great extent simulate behaviour during the real industrial process. The aerosol could better represent in situ poisoning and therefore give a more realistic picture of the effect of potassium. This knowledge will be useful for designing new BTL processes. 5. ConclusionAerosol technology was used as a new method for depositing potassium salts on the Co surface. Poisoned catalysts were tested in Fischer Tropsch synthesis reactor together with elemental analysis. Results are compared to the reference catalyst and with previous work which use IWI as poisoning method. 6. References[1] A. Norheim, D. Lindberg, J. E. Hustad, and R. Backman, Energy and Fuels, (2009)[2] E. S. Wangen, A. Osatiashtiani, and E. A. Blekkan, Top. Catal., (2011)[3] C. M. Balonek, A. H. Lillebø, S. Rane, E. Rytter, L. D. Schmidt, and A. Holmen, Catal. Letters, (2010)[4] E. A. Blekkan, A. Holmen, S. Vada, Acta Chem. Scand., (1993)[5] J. Gaube and H. F. Klein, Appl. Catal. A Gen., (126–132, 2008)[6] H. M. Westberg, M. Byström, and B. Leckner, Energy and Fuels, (18–28, 2003)[7] S. Albertazzi, F. Basile, J. Brandin, J. Einvall, G. Fornasari, C. Hulteberg, M. Sanati, F. Trifirò, and A. Vaccari, Biomass and Bioenergy, (2008)[8] A. H. Lillebø, E. Patanou, J. Yang, E. A. Blekkan, and A. Holmen, in Catalysis Today, (2013)[9] E. Patanou, A. H. Lillebø, J. Yang, D. Chen, A. Holmen, and E. A. Blekkan, Ind. Eng. Chem. Res., (2014)[10] J. Einvall, S. Albertazzi, C. Hulteberg, A. Malik, F. Basile, A. C. Larsson, J. Brandin, and M. Sanati, Energy and Fuels, (2007)
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