Iu dasagrds TI vonnnereerennnnctneee aes ‘Symposium on Advances in Fischer-Trops sch Chemistry Presented Before the Division of Petroleum Chemistry, Inc. 219th National Meeting, American Chemical Society San Francisco, CA, March 26-31, 2000 ee Fischer-Tropsch Catalysis Isomerization of 1-Alkene during Iron Catalyzed Buchang Ski, Rober J. O'Brien, Shigi Bao, Liguang Xu and Burtron H. Davis Center for Applied Energy Research University of Kentucky 12540 Research Park Drive Lexington, KY 40511 INTRODUCTION 'A double bond rearrangement can take place on treatment with ston base In this case, the mechanism involves abstraction by base to generate 8 a vson which then combines with a proton to reform an alkene, PY carbaioW ith an acid, double bond rearrangements can also occur. The treat erin this case is the formation of a carbocation and results in the aa pond migration after losing another proton. There are many way fo" dou bond isomerization to take place inchuding photochemical reactions Ghd by treatment with metal ions (). In these cases the hy r9g8% transfer and bY len electron pair. Thus, the hydrogen that is added or lost does «© involves 37 fgon pair or the absence of an electron pair. The mechanism in Trace reactions is dictated by the species acting in the initiation step; °~ these re" this is the addition of an electron-pair deficient acid or a proton abstracting electron-pair rich base. Inthe presence of metal catalysts, the hydrogenation of a L-alkene is ‘often accompanied by double bond ‘migration and cis-trans isomeriza- tion. For the homogeneous catalyzed reaction, at least two mechanisms hhavebeen recognized for the isomeri- zation ofthe alkene in the presence of ‘a metal complex: the metal hydride ‘addition elimination mechanism and the w-allyl complex mechanism (1, 2). ‘These two mechanisms require that hydrogen dissociate by heterolytic ond breaking to form a proton and a hydride ion. However, for metallic catalysis the bond breaking is usually considered tobehomolyticso thatthe breaking of the hydrogen bond forms two hydrogen atoms with an electron thatis utilized in bonding to themetal surface. Thus, metal catalyzed hydro- ggenation and /or isomerization reac- ions are usually considered to be, oF to resemble, a mechanism that in- volves a radical intermediate (3). In the iron catalyzed Fischer- ‘Tropsch synthesis (FTS), a mixture of alkane, alkene, cis- and trans-2- alkenes, more internal alkenes, and ‘oxygenates of each carbon number may be formed. 1-Alkenes can be ‘The fraction of the internal thatare primary products remains an ‘unanswered question. Many investi- gators consider Lalkene tobe the pri- mary alkene product and that the on internal alkenes arise from an isomerization product. Jn this study, T-octene-dis was introduced into the reactor together ‘with the synthesis gas. The product distribution and the deuterium distri- ‘bution of each compound derived from L-octene-dis provides informa tion about the isomerization mecha nism and its contribution relative to its hydrogenation. EXPERIMENTAL ‘The FITS was carried out as de- scribed previously (13-23). The iron catalyst (100Fe:4 4Si:1.4K atomic ra- tio) was activated using CO and the synthesis was conducted at 175 psig land 270°C. 1-Octene-dis (5g diluted ‘with 20g o-xylene) was added to the iter autoclave during five. Imme- diately prior to adding 1-octene-di6, the three product traps were emp- tied, At the end of the addition of Lroctene-dis, the product traps were drained and drained again after 19h. ‘The deuterium content of nroctane ‘and the octene isomers was deter- mined using g.c-mss. The data were ‘corrected for the "°C content of the products. RESULTS AND DISCUSSION ‘The data in Table 1 provide the ‘composition of the deuterium-con- taining Cerproducts collected at the end of theSh addition of 1-octene-dis ‘and the sample collected 19 h later. {-Octene-dis was isomerized to deu- terium-containing cis- plus trans-2- foctene and hydrogenated to deuterium-containing n-octane. The extent of conversion, as expected, ‘was greater in the sample collectedafter 19 h than the sample collected immediately after termination of 1- octene-dig addition. The ratio of cis- to trans-2-octene is essential 1, indi- cating no steric preference for the ab- straction of the H(D) that leads to the 2-octene product. ‘The cistransratioof theisomeriza- tionproduct depends upon the catalyst (26-28). For the RhH(CO)(PPhs)3 cata- lyzed isomerization of I-butene in benzene, the ratio of trans:cis is 60:33, (29). The mechanism for this reaction is believed to occur through a r-allyl Table 1. ‘The Niole% of Hydrogenation and Isomerization of added 1-Octene-dis ‘under ron Catalyzed Hydrocarbon Synthesis Conditions ‘Mol% (Sts on stream) —[_Mol¥ (24s on seam) octane 859) 65 octane 80 208. wane Doctane 30 7 eis 2octane 3a 56 Table2. Deuterium Distribution in Octenes 1-Octene Trans-2-Octene Cis2-Octene Staring | Shrs.on | 24s on | Stra. on | 24 re. on | Sts. on | 28 he on Reagent | Seam | “Sueam | Steam | Sueam | Steam | Saeam px | sss | 7 | om | ws | ms | os | esa pmo | iss | us | ue | w2 | m4 | 2 | oe cp. | 7s [os | us | o 0 ° ° cpu | 28 | ss | 2a | aa | ia | 396 | m5 cut | 16 | 2 | ons | 364 | ose | 393 | 297 cDuHs | 0 107 | 29 | 208 | s24 | iso | 2n6 Dall, ee 16s | 3a_| 172 cDuty | 0 ° 24 2 52 ° ° Table3. Deuterium Distribution in Octane ‘3 Hrs On Sueam 24s On Seam Dy 947 ‘Dis! 152 Dut 40 DH 372. 259 De 34 28 DSH, 97 243 Dats 78. Co 58 ant complex mechanism: the ratio results from the higher stability of the syn-n- allyl complex relative to the anti-n-al- lyl complex. In contrast, the metal hydride addition-elimination mecha- nism cis/trans ratio greatly exceeds the equilibrium ratio because of the greater stability of the cis-alkene- metal complex relative to the trans- alkene-metal complex (30, 31). Since the ratio of the cis/trans 2-alkene iso- mersis about 1 itappears thatneither of these mechanisms apply for the isomerization. ‘The data in Table 2 indicate that there is H/D exchange in the added L-octene-dis that was recovered with the reaction mixture. The deuterium content of the added 1-octene-dis was 98.5%, corresponding to 15.8 deuterium per molecule. The sample collected after Sh of adding 1-octene~ dig contained 92.7% deuterium, cor- responding to 148 deuterium per molecule. For the sample collected af- ter 19h, there was only 87.1% deute- rium, indicating that less than two deuterium had been replaced by hy- drogen, The most exchanged iso- topomer that could be detected in the sample collected after 19 h was 1-oc- tene-di1, corresponding to the ex- change of five deuteriums with hydrogen. The distribution of the hy- drogen in the isotopomers of l-octene in both samples are consistent with the exchange occurring in a series of steps, each involving the exchange of ‘one deuterium with a hydrogen. In this experiment, the hydrogen iso- tope in the hydrogen added with the synthesis gas and in the added o- xylene was present in a much greater amount than the deuterium (25:1 for theSh sample and close to300:1 in 19 hi sample). Assuming rapid surface mobility of the H(D) so that the hy- drogen isotopomers on the surface are equilibrated, any exchange should add hydrogen. The distribu- tion of hydrogen implies that the desorption of the alkene is more rapid than the exchange with hydro- gen; if this was not the case we would expect multiple exchange with each adsorbed deuterium containing spe-“(ess cag-19¢ dd 980A MON HOR cesqjang uspssonuy ASTIN Y sperma B10 'aPv TEN (D GaL1> SUALVUSLIT Apr uayl JO apreomuouniao> atp PUP g0CdrLTeE Meowac equine weno? 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S72 roe auayoo-7-suen pue -S SURE -uoosumainap af Od HUES SE ‘aures axp 0} papyod UIEU Br juawnesy 99190 AH PUE PIACUAT anwamap ap wig wow UE was “Expaur woReZsrewost TenoajOWen “hie saywuramya SP-2UI0-7 STEN Jo sy xeupa jo aouasqe oul -onp-s1ay20-1 UeHp P2GEOSPE fqBuons 21015 5] ODER PUESTP ITY ‘Sort pappt axp WEUA HNCUTE ELON sp euou2s kao * z qotentiatg SEE HD HADFED"AFD zQ) Olah, G.A., Molnar, A., (14) Dabbagh, H,, Tau, L.-M, Bao, (23) Xu, L., Bao,S, Houpt, D. J, “Hydrocarbon Chemistry, S,, lalasz, J. and Davis, B. H., Lambert, S.J. and Davis, John Wiley & Sons, pp 118-128 Fischer-Tropsch synthesis: B. H,, Catal. Today, 36,347 (1995). Comparison of product selec- 1997). tivity and “4C labeled ethanol (3) Bond, G.C,, “Catalysis by Met- incorporation at one and (24) Herrington, E. F, Chem. Ind,, als," Academic Press, New seven atmosphere conditions, 347 (1946). York, 1962. "Catalysis 1987" (. Ward, Ed.) Elsevier, Amsterdam, pp.61- (25) Iglesia, E,, Reyes, S.C. and (4) Podgurski, H. 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