ELSEVIER Applied Catalysis A: General 214 (2001) 77-86 APPLIED CATALYSIS. GENERAL wowelvierconMoestpesta Effect of reaction conditions on the product distribution during Fischer-Tropsch synthesis over an industrial Fe-Mn catalyst Yuan-Yuan Ji, Hong-Wei Xiang, Ji-Li Yang, Yuan-Yuan Xu, ‘Yong-Wang Li*, Bing Zhong Group of Catalytic Kinetics and Theoretical Modeling, State Key Laboratory of Coal Comersion Instat of Coal Cher: Chinese Academy of Sciences, FO. Bax 165, Taiyuan 030001, PR China Received & August 2000; recive in revised frm 18 December 2000; aceepieé 25 December 2000 Abstract ‘The product distibutions of Fischer-Tropsch synthesis (FTS) over an industrial Fe-Mn catalyst are investigated under differem reaction conditions in an integral fixed bed reactor. The typical non-ASF distributions of the FTS products are analyzed in tems ofthe competitive steps of the surface reactions, and the desorption, diffusion and re-adsorption of alkenes ‘under these broad reaction conditions. Ii found that alkene selectivities are significantly higher than those for alkanes in ‘broad chain length range from C: to about Cap over the Fe-Mn catalyst under most reaction concitions. Under the operation conditions ofthe catalyst, alkenes with carbon number lrger than 27 cannot be detected inthe wax products. Consequently, the contents of heavy alkanes have a slight increase at about Cy, implying that primary alkenes with chain longer than Coy are dominantly hydrogenated to alkanes due tothe long residence time ofthe products in the catalyst pores. © 2001 Elsevier Science B.V. All rights reserved, ‘Keywords: Fisher-Tropsh synthesis; Produtdistibution; Fe Ma etalyt; Resorption of akenes 1. Introduction Production of hydrocarbons from syngas through Fischer-Tropsch synthesis (FTS) has attracted much attention in both catalysis and chemical engineering fields during the last century, due to the potential of the technology providing an optional route for liquid fuel production, which has been the backbone of the ‘modern economic development [1.2]. The high quality * Corresponding author. Tel+86-38)-4088261; fax: +862351-4050520, Email address: yw @pabliessax.en (Y- "Li, FTS productas fuel has been proven tobe environmen- tally friendly compared with those from conventional crude oil route, for example, Shell's SMDS technology hhas been able to provide high quality diesel products (3,4). Another factor repealing FTS as an important technique is the fact that the rich supplies of coal and natural gas as the feed of FTS complexes in the world may provide more sustainable carbon resources forthe ‘economic development of the world in the future [5,6]. With the development of Fischer-Tropsch syn- thesis, the quantitatively description of its product distribution has continuously been improved. In 1946, Herington first treated the FTS product distribution (0826-860X/015 ~ see font mater © 2001 Elsevier Science BLY. All sights reserved PIL: $0926-860X(01)00480-X COPY* YW. I et al “Applied Catalyis A: General 216 (2001) 77-86 in terms of a polymerization mechanism (7). Later, ‘the Aderson-Schluz-Flory (ASF) equation was es- tablished and/or recognized [8,9]. The ASF scheme describes a phenomenon that the chain propagation and the termination probabilities are independent ‘of carbon mumber. This product distribution law was in vogue for @ long time [8-10]. And the de- vations (if any) from the ASF distribution were then attributed to experiment errors and artifacts 10,1). In 1967, Pichler et a. first reported a deviation from ASF distribution (12). In fact, the evidence had been observed as early as 1943 [13]. Since 1980, more and more results of non-ASF distributions have been reported [14-17], including the data of Satter ficld, which had been reported as the ASF distribution and was later re-examined and concluded to be a non-ASF one [10,18]. Non-ASF distributions show that the chain propagation and termination probabil ities are not independent of carbon number [18-22). However, many considerations remained in ASF the- ‘ory. For example, the product distribution data were frequently treated by the superposition of two ASF 1) in feed lead to low yield of alkanes in Region IV, im- plying'a dominant effect on the suppression of chain ‘growth, At this point, we should be aware that the residence time on catalyst surface and/or in the cata- lyst pores for the heavy products inthis region is very Tong, namely all the alkenes primarily formed have sufficient time to undergo re-adsorption and further to be slowly hydrogenated into alkanes. However, the ef- fect of separation of active carbon species on surfaces by rich surface hydrogen species is distinguishably reflected till this region. On the other hand, the formation of long chain active carbon species on surface is thermodynamically preferential at low H2/CO ratio in feed. Meanwhile, high CO partial pressure in the reactor (correspond- ing to low Hz/CO ratio) is not preferential for the re-adsorption of alkenes [31,38]. This leads to the low selectivity for light products but the high selectivity for heavy alkenes in Region II-II,, which agrees with the literature elucidation (though rather superficial) (31,37), For the alkanes in Region IU, similar reasons can be applied for any feasible explanation. In genera, alkenes in Region III clearly increase ‘with the decrease of Ha/CO ratio in feed, while alkanes. in the same regions do not clearly change with Ha/CO ratio in feed. When carbon numbers are so large (larger than Coy in our tests) that all active species are ultimately hydrogenated to alkanes, alkenes vanish in Region IV [20,33]. The restriction that low Ha/CO ra- tio is not preferential for hydrogenation does not play its role any more. Consequently, alkanes in Region IV, the same as heavy alkenes in Region Il and IL, in- crease with the decrease of Hz/CO ratio in feed. Due to the elimination of alkenes, all carbon species are hydrogenated to alkanes, leading tothe noticeable in- crease of Czy alkane (the reason is same for Figs. 3-6). It is indicated (Figs. 3 and 4) that C)~Ce alkenes and alkanes increase with the increase of reaction temperature. This may be the reason that high temper- ature is preferential for chain termination and removal of alkenes. Therefore, the contents of both alkenes ‘and alkanes in Region I increase with the increase of ‘temperature. Meanwhile, the competition of the steps in the catalystic cycle of FTS leads to the general increase of heavy hydrocarbons from Region II to IV. Itis indicated in Fig. 5 that C}Ce alkenes unnotice- ably change with space velocity, especially at higher space velocity. This is mainly due tothe fact that these: light products in Region I have high volatilities. and, hence, are not influenced by the diffusion limitations which, if any, should have been resolved by the change: of space velocity. In contrast, heavy alkenes: (Ce). significantly change with space velocity. It.is.con- cluded that the diffusion effect plays a dominant role in the removal of alkenes from the eatalyst surface for heavy alkenes from Region Il, indicating that exter- nal mass transfer limitation is not eliminated at space velocity less than 14000h~" forall heavy products. For all heavier products, at the low space veloc- ity, the external diffusion resistance is large, which hinders the removal of alkene products from catalyst surface and/or catalyst pores efficiently and, there- fore, enhances the re-adsorption of and secondary reactions of alkenes, making the possibility for hydro- ‘genation higher and leading to low contents of alkene oducts. At he high space velo, he extemal if resistance is small, therefore, this enhances the rrmoal of sere products from the catalyst surface ‘and suppresses the alkene re-adsorption, leading to high contents of alkene product. It should be noted that, as we can observe in Fig. 6, alkane distributions, slightly change with space velocity. The phenomena ‘cannot be easily interpreted. Further investigation of intrinsic reasons, such as rate constant, to elucidateWoW. Jie al /Applied Catalysis A: General 214 (2001) 77-86 as all the phenomena in detail, requires systematical kinetics analysis, which is our ongoing work. 5. Conclusion It is observed that the carbon number regions in product distributions are related to physical properties. ‘of hydrocarbons. Although now the relationship can not be accurately evaluated, our explanations for the systematical experimental data have projected multi- ple kinetic factors to the understanding of the nature of the Fischer-Tropsch product distribution. For alkene distributions, it is readily concluded that: (@) low H2/CO ratio in feed is preferential for the increase of heavy alkenes and high Hz/CO ratio in feed is preferential for the increase of light alkenes; (©) low temperature is preferential forthe increase of heavy alkenes and high temperature is preferential for the increase of light alkenes; (c) high space velocity is preferential forthe increase of heavy alkenes, while space velocity has no significant influence on light alkenes. It is found that the effectiof reaction con- ditions (H2/CO ratio in feed, temperature and space velocity) on the whole alkene distributions is signif- icantly in accordance with the thermodynamics and Kinetics of Fischer—Tropsch synthesis: However, the effects of Hz/CO ratio infeed and of space velocity on heavy alkane distributions are notsignificant on this catalyst. Since alkene re-adsorption seriously affects product selectivity, the effect of alkene re-adsorption, which is also affected by the reaction conditions, on product distributions has to be simultaneously consid- ered when the effect of reaction conditions on product distributions is investigated, ‘We have explained the observed product distribu- tions by taking into account the deeply implied factors from both thermodynamics and kinetics by classify- ing the products as fractions. This is the first stage of. cour ongoing detailed kinetic modeling of this process. Acknowledgements ‘The authors acknowledge the financial support from the Chinese Academy of Sciences through the basic research project (Beiren Jihua-B) and the FTS development project and the National Natural Science Foundation of China (No. 29673054). In addition, ‘one of the authors (¥.-W. 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