Carbon number Flory kinetics

Hydrocarbon distributions in the Fischer-Tropsch (FT) synthesis on Ru, Co, and Fe catalysts often do not obey simple Flory kinetics. Flory plots are curved and the chain growth parameter a increases with increasing carbon number until it reaches an asymptotic value. a-Olefin/n-paraffin ratios on all three types of catalysts decrease asymptotically to zero as carbon number increases. These data are consistent with diffusion-enhanced readsorption of a-olefins within catalyst particles. Diffusion limitations within liquid-filled catalyst particles slow down the removal of a-olefins. This increases the residence time and the fugacity of a-olefins within catalyst pores, enhances their probability of readsorption and chain initiation, and leads to the formation of heavier and more paraffinic products. Structural catalyst properties, such as pellet size, porosity, and site density, and the kinetics of readsorption, chain termination and growth, determine the extent of a-olefin readsorption within catalyst particles and control FT selectivity. 

Flory polymerization kinetics (4). Henrici-Olive and Olivd (5) proposed the use of the related equation of Schulz (6). Over the last decade the Flory equation has been used frequently to describe product distributions in FT synthesis. The Friedel-Anderson (i) or Flory (4) approaches apply when the rates of propagation and termination are independent of carbon number. We do not attempt here to discuss all previous research on FT product distributions except to say that the literature contains many examples of product distributions that obey Flory kinetics within relative narrow carbon number ranges and many that do not. 

Carbon number distributions are similar on all Co catalysts. As on Ru catalysts, termination probabilities decrease with increasing chain size, leading to non-Flory product distributions. The modest effects of support and dispersion on product molecular weight and C5+ selectivity (Table III) reflect differences in readsorption site density and in support pore structure (4,5,14,40,41), which control the contributions of olefin readsorption to chain growth. Carbon number distributions obey Flory kinetics for C30+ hydrocarbons the chain growth probability reaches a constant value (a ) as olefins disappear from the product stream. This constant value reflects the intrinsic probability of chain termination to paraffins by hydrogen addition it is independent of support and metal dispersion in the crystallite size range studied. 

The high asymptotic value of C5+ selectivity at large values of occurs on pellets that restrict the removal of reactive a-olefins and allow many readsorption events in the time required for intrapellet olefin removal by diffusion. Yet, transport restrictions within these pellets must not significantly hinder the rate of arrival of CO and H2 reactants to the active sites. Carbon number distributions also obey Flory kinetics for high values of because even the smaller olefins significantly react within a catalyst pellet. 

Our readsorption model shows that carbon number distributions can be accurately described using Flory kinetics as long as olefin readsorption does not occur (/3r = 0), because primary chain termination rate constants are independent of chain size (Fig. 24). The resulting constant value of the chain termination probability equals the sum of the intrinsic rates of chain termination to olefins and paraffins (j8o + Ph)- As a result, FT synthesis products become much lighter than those formed on Co catalysts at our reaction conditions (Fig. 24, jSr = 1.2), where chain termination probabilities are much lower than jS -I- Ph for most hydrocarbon chains. The product distribution for /3r = 12 corresponds to the intermediate olefin readsorption rates experimentally observed on Co/Ti02 catalysts, where intrapellet transport restrictions limit the rate of removal of larger olefins, enhance their secondary chain initiation reactions, and increase the average chain size of FT synthesis products. 

Carbon number distribution plots also become linear when olefins readsorb very rapidly (large /3r) or when severe intrapellet transport restrictions (large ) prevent their removal from catalysts pellets before they convert to paraffins during chain termination (Fig. 24, jSr = 100). In this case, chain termination to olefins is totally reversed by fast readsorption, even for light olefins. Chain termination occurs only by hydrogen addition to form paraffins, a step that is not affected by secondary reactions and for which intrinsic kinetics depend only on the nature of the catalytic surface. The product distribution again obeys Flory kinetics, but the constant chain termination probability is given by )8h, instead of po + pH- Clearly, bed and pellet residence times above those required to convert all olefins cannot affect the extent of readsorption or the net chain termination rates and lead to Flory distributions that become independent of bed residence time. 

Based on an experimental study the present investigation addresses for two different types of catalysts the effect of CO2 concentration in the reaction gas on carbon conversion rates, yields of organic products and selectivity in the carbon number range Cj to 20- Two catalysts on Fe- and Co-basis with significantly different CO shift reaction activity were characterized by parameters according to the previously developed model of non trivial surface polymerisation , based on extended Anderson-Schulz-Flory kinetics [2]. 

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