The mechanism of chain growth in the Fischer-Tropsch hydrocarbon synthesis

1988 ◽  
Vol 1 (10) ◽  
pp. 307-310 ◽  
Author(s):  
Richard W. Joyner
2018 ◽  
Author(s):  
Richard Kong ◽  
Mark Crimmin

<i>The formation of carbon chains by the coupling of COx (X = 1 or 2) units on transition metals is a fundamental step relevant to Fischer-Tropsch catalysis. Fischer-Tropsch catalysis produces energy dense liquid hydrocarbons from synthesis gas (CO and H2) and has been a mainstay of the energy economy since its discovery nearly a century ago. Despite detailed studies aimed at elucidating the steps of catalysis, experimental evidence for chain growth (Cn to Cn+1 ; n > 2) from the reaction of CO with metal complexes is unprecedented. In this paper, we show that carbon chains can be grown from sequential reactions of CO or CO2 with a transition metal carbonyl complex. By exploiting the cooperative effect of transition and main group metals, we document the first example of chain propagation from sequential coupling of CO units (C1 to C3 to C4), along with the first example of incorporation of CO2 into the growing carbon chain.</i><br>


2011 ◽  
Vol 346 (1-2) ◽  
pp. 55-69 ◽  
Author(s):  
Dong-Bo Cao ◽  
Yong-Wang Li ◽  
Jianguo Wang ◽  
Haijun Jiao

2017 ◽  
Vol 682 ◽  
pp. 115-121 ◽  
Author(s):  
Yifan Wang ◽  
Ying Li ◽  
Shouying Huang ◽  
Jian Wang ◽  
Hongyu Wang ◽  
...  

2016 ◽  
Vol 120 (51) ◽  
pp. 29210-29224 ◽  
Author(s):  
C. J. Weststrate ◽  
Ionel M. Ciobîcă ◽  
Jan van de Loosdrecht ◽  
J. W. Niemantsverdriet

Author(s):  
Luis A. Díaz-Trujillo ◽  
Gilberto Toledo-Chávez ◽  
Gladys Jiménez-García ◽  
Héctor Hernández-Escoto ◽  
Rafael Maya-Yescas

AbstractThe main goal of this paper is to critically review current microkinetics available for Fischer-Tropsch synthesis (FTS) modelling, in order to propose the best way to follow this set of complex reactions; therefore a microkinetic model was developed for FTS, accomplishing surface chemistry, heterogeneous kinetics, and single-event previous development for Co-based catalysts. Model starts simulating CO activation on catalyst surface, and then formation of methane, ethane and subsequent chain growth. Reaction rates were derived following the formalism of Langmuir-Hinshelwood-Hougen-Watson (LHHW); surface steps were proposed in consequence of feasibility. Chain growth was modelled by single-event steps, taking into account geometrical conformation explicitly. Number of growth steps of 1-olefins was rectified as requiring one more active site than mechanisms proposed previously; it was found that formation of these olefins exhibits a fast drop in chain growth; this phenomenon is explained in terms of probable geometrical conformations that lead to the number of single events. Experimental results in literature about isothermal synthesis of hydrocarbons in the gasoline range were simulated in a fixed-bed laboratory reactor; thermodynamic consistency was derived from chemical equilibrium over all reactions occurring during FTS. Equilibrium constants were evaluated as function of Gibbs free energy, and partial pressures of reactants and products.


Author(s):  
Xun Wang ◽  
Yunhan Xiao

A co-production system based on FT synthesis reactor and gas turbine was simulated and analyzed. Syngas from entrained bed coal gasification was used as feedstock of low temperature slurry phase Fischer-Tropsch reactor. Raw synthetic liquid produced was fractioned and upgraded to diesel, gasoline and LPG. Tail gas composed of unconverted syngas and F-T light component was fed to gas turbine. Supplemental fuel (NG, or refinery mine gas) might be necessary, which was dependent on gas turbine capacity, expander through flow capacity, etc. FT yield information was important to the simulation of this co-production system. A correlation model based on Mobil’s two step pilot plant was applied. This model proposed triple chain-length-dependent chain growth factors and set up correlations among reaction temperature with wax yield, methane yield, and C2-C22 paraffin and olefin yields. Oxygenates in hydrocarbon phase, water phase and vapor phase were also correlated with methane yield. It was suitable for syngas, iron catalyst and slurry bed. It can show the effect of temperature on products’ selectivity and distribution. Deviations of C5+ components yields and distributions with reference data were less than 3%. To light gas components were less than 2%. User models available to predict product yields, distributions, cooperate with other units and do sensitive studies were embedded into Aspen plus simulation. Performance prediction of syngas fired gas turbine was the other key of this system. The increase in mass flow through the turbine affects the match between compressor and turbine operating conditions. The calculation was carried out by GS software developed by Politecnico Di Milano and Princeton University. The simulated performance assumed that the expander operates under choked conditions and turbine inlet temperature equals to NG fired gas turbine. A “F” technology gas turbine was selected to generate power. Various cases were investigated so as to match FT synthesis island, power island and gasification island in co-production systems. Effects of CO2 removal/LPG recovery, co-firing, CH4 content variation were studied. Simulation results indicated that more than 50% of input energy was converted to electricity and FT products. Total yield of gasoline, diesel and LPG was 136g-155g/NM3(CO+H2). At coal feed 21.9kg/s, net electricity exported to grid was higher than 100MW. Total production of diesel and gasoline (and LPG) was 118,000 tons(134,000tons)/Year. Under economic analysis conditions assumed in this paper, co-production system was economic feasible. The after tax profits can research 17 million EURO. Payback times were ranged from 6-7 years.


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