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Experimental and kinetic modeling of Fischer–Tropsch synthesis over nano structure catalyst of Co–Ru/carbon nanotube

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Abstract

In this work, the nanostructure catalyst of Co–Ru/CNTs is prepared by chemical reduction technique. Then, a set of catalytic experiments are designed and conducted for the Fischer–Tropsch synthesis (FTS) using the synthesized catalyst in a fixed bed reactor. The physical and chemical properties of the support and the synthesized catalyst were determined using the BET, XRD, H2–TPR, TEM, and H2-chemisorption characterization techniques. Based on the alkyl mechanism and using the Langmuir–Hinshelwood–Hougen–Watson (LHHW) isotherm, a kinetic model is developed for FTS. In most of the previous kinetic models, the primary reactions have merely been used, but in the current derivation of the developed kinetic model, the secondary reactions (adsorption, hydrogenation and chain-growth) and re-adsorption of primary olefins at the secondary active sites are considered. The present comprehensive kinetic model is applied for the product distribution such that the rate equations parameters are acquired via optimization. To estimate the kinetic model parameters, FTS was accomplished via a series of tests under the operating conditions as pressure (P): 10–20 bar, temperature (T): 483–513 K, gas hourly space velocity (GHSV): 1400–2400 h−1 and the H2/CO ratio of 1–2. The rationality and significance of the suggested model were checked through the statistical and correlation tests. The obtained results indicated that the outcomes of the current kinetic model were in good agreement with the experimental data. Using the present kinetic model, the average absolute deviations (AAD%) for the prediction of methane, ethylene and heavier hydrocarbons (C5+) formation rates are obtained as 7.06%, 11.57% and 14.74%.

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Abbreviations

FTS:

Fischer–Tropsch synthesis

LHHW:

Langmuir–Hinshelwood–Hougen–Watson

CNTs:

Carbon nanotubes

ASF:

Anderson–Schulz–Flor

F-B:

Fixed-bed reactor

TPR:

Temperature-programmed reduction

XRD:

X-ray diffractometer

TEM:

Transmission electron microscopy

RDS:

Rate-determining step

FWHM:

Full width half maximum

R:

Universal gas constant (8.314 × 10−5 bar m3/mol K)

x:

Position within the catalyst bed

T:

Reaction temperature (K)

t:

Time consuming for Fischer–Tropsch reaction (s)

Mw,j :

Molecular weight of component j

P:

Productivity (kg) (mass of produced hydrocarbon in liquid phase product)

F:

Molar flow of product in gas phase (mol/s)

rj :

Formation rate of component j (mol/kg s)

yj :

Molar fraction of component j in gas phase

wj :

Weight fraction of component j in the liquid phase

W:

The catalyst weight (kg)

FCO,in :

Molar flow of carbon monoxide in the reactor inlet (mol/s)

FCO,out :

Molar flow of carbon monoxide in the reactor outlet (mol/s)

B:

FWHM of the Co3O4 at diffraction peak of 2θ = 36.8

MC,out :

Mass of output carbon

MC,in :

Mass of input carbon

NC :

Total number of the species

Fj :

Mole flow rates of jth component (mol/s)

Ri :

Rate of ith reaction (mol/kg s)

NR :

Number of total considered reactions

XCO :

CO conversion (%)

PT :

Total pressure in the reactor (bar)

Pj :

Partial pressure of j component (bar)

O:

Objective function of FTS reaction

K1 :

Equilibrium constant for the H2 adsorption on the primary active site

E:

Reaction activation energy (kJ/mol)

k3 :

Rate constant of chain growth in FTS mechanism for primary active site (mol/kg s)

k3,0 :

Pre-exponential factor of chain growth in FTS mechanism for primary active site (mol/kg s)

k5 :

Rate constant of the formation of methane (mol/kg s)

k5,0 :

Pre-exponential factor of the formation of methane (mol/kg s)

k4 :

Rate constant of the formation of paraffins on primary active site (mol/kg s)

k4,0 :

Pre-exponential factor of the formation of paraffins on primary active site (mol/kg s)

k6 :

Rate constant of the formation of olefins (mol/kg s)

k6,0 :

Pre-exponential factor of the formation of olefins (mol/kg s)

K7 :

Equilibrium constant for the CO adsorption on the secondary active site

k10 :

Rate constant for the forward reaction of olefin re-adsorption (mol/kg s bar)

k10,0 :

Pre-exponential factor for the forward reaction of olefin re-adsorption (mol/kg s bar)

k−10 :

Rate constant for the reverse reaction of olefin re-adsorption (mol/kg s)

k−10,0 :

Pre-exponential factor for the reverse reaction of olefin re-adsorption (mol/kg s)

k11 :

Rate constant of chain growth in FTS mechanism for secondary active site (mol/kg s)

k11,0 :

Pre-exponential factor of chain growth in FTS mechanism for secondary active site (mol/kg s)

k12 :

Rate constant of the formation of paraffins on secondary active site (mol/kg s bar)

k12,0 :

Pre-exponential factor of the formation of paraffins on secondary active site (mol/kg s bar)

ψ:

Primary active site on catalyst surface

θ:

Secondary active site on catalyst surface

σji :

Stoichiometric coefficient of jth component in ith reaction

αn :

Chain growth factor of FTS reaction for carbon number (n > 1)

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Authors and Affiliations

  1. Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran

    Ali Haghtalab & Jafar Shariati

  2. Department of Chemical Engineering, Tafresh University, P.O. Box 79611-39518, Tafresh, Iran

    Amir Mosayebi

Authors
  1. Ali Haghtalab
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  2. Jafar Shariati
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  3. Amir Mosayebi
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Correspondence to Ali Haghtalab.

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Haghtalab, A., Shariati, J. & Mosayebi, A. Experimental and kinetic modeling of Fischer–Tropsch synthesis over nano structure catalyst of Co–Ru/carbon nanotube. Reac Kinet Mech Cat 126, 1003–1026 (2019). https://doi.org/10.1007/s11144-019-01535-7

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