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Open-loop response of Fischer–Tropsch reactions to manipulation of temperature and pressure

  • Salvador Piña-Contreras , Gladys Jiménez-García ORCID logo , Héctor Hernández-Escoto ORCID logo und Rafael Maya-Yescas ORCID logo EMAIL logo
Veröffentlicht/Copyright: 21. November 2024
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International Journal of Chemical Reactor Engineering
Aus der Zeitschrift International Journal of Chemical Reactor Engineering Band 22 Heft 11

Abstract

In the present work, the Fischer–Tropsch synthesis (FTS) is carried out through simulation. This reaction uses a gas mixture, called synthesis gas, composed of carbon monoxide rich in hydrogen (H2/CO > 2.5), to form medium and long chain hydrocarbons (C5 +). For the modeling of this system, a packed bed reactor with a cobalt-based catalyst has been considered, which promotes the polymerization of methylene species, selective to linear paraffins and 1-olefins. The objective of this work is evaluating the impact of operation variables, such as feed flows and temperature, coolant flow, system pressure, on the chain length distribution of the products. Current operating policies does not promote selectivity to the production of synthetic gasolines (C5–C12), because of the drastic increase in the temperature inside the reactor as consequence of the high exothermicity of the reactions (ΔH = −170 kJ mol−1). It has been impossible to maintain these reactions within the appropriate temperature range (475–520 K) without the presence of an external agent that manages the available heat, for this project molten sales have been proposed as a cooling medium (KNO3–NaNO3), based on its favorable heat transfer characteristics. By analyzing the system responses, the open loop model has allowed us to explore multiple hydrocarbon production scenarios, specifically highlighting the increasing of the yield of synthetic gasoline (48 wt%) in the products, from a defined molten salts (coolant) countercurrent flow range (7.05E-2 at 2.50E-1 m/h). It was noticed that this heat management allowed us to obtain a specific range of hydrocarbons, representing the opportunity to control the growth of the chain length. In conclusion, this analysis will lay the foundations for the design control policies, which help to increase current yields of synthetic gasoline, making it possible to achieve the desired quality for the immediate future.

Keywords: mass and energy balances; Fischer–Tropsch synthesis; open loop response; tubular reactor
Corresponding author: Rafael Maya-Yescas, Facultad de Ingeniería Química, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia, Michoacán de Ocampo, 58030, México, E-mail:

Acknowledgments

SPC fully thanks the CONAHCYT scholarship 922918 for PhD studies. GJG, HHE and RMY greatly appreciate the grants from the National System of Researchers (CONAHCYT-SNII).

  1. Research ethics: The manuscript is based on our original work, devoted to the deeper study of the chemical reactors. This work has not been sent to anywhere else for publication. A previous version was presented at the IEC-23 in Zacatecas, México.

  2. Informed consent: Not applicable.

  3. Author contributions: Salvador Piña-Contreras, PhD student and main author. Gladys Jiménez-García, PhD co-supervisor, theoretical support and revision. Héctor Hernández-Escoto, advisor of the project, theoretical support and revision. Rafael Maya-Yescas, main PhD supervisor, leader of the research project, theoretical support and revision. The authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: Internal founding by the research project CIC-20.20 at the Universidad Michoacana de San Nicolás de Hidalgo.

  7. Data availability: The raw data can be obtained on request from the corresponding author.

Appendix 1: Notation

Latin characters
C co Carbon monoxide concentration mol/h
C H2 Hydrogen concentration mol/h
C i Concentration of the i-th specie, i = 1…n. mol/h
C T Total concentration mol/h
C P ‾ Average heat capacity kJ/g K
C Pi ‾ Heat capacity by species, i = 1…n. kJ/g K
D R Reactor diameter M
d R Internal diameter M
d wall Wall thickness M
E Ak Activation energy of the k-th reaction step kJ/mol
F i Flow of the i-th specie, i = 1…n. mol/h
F T Total flow of products mol/h
k j Frequency factor of the j-th reaction step Appropriate
K j Equilibrium constant of the j-th reaction step Appropriate
M i Molecular weight Da
P o Initial pressure MPa
P i System pressure variation MPa
r i Radial position M
r k Reactor radius M
t Time H
T Temperature inside the reactor K
T J Coolant temperature K
T Ref Reference temperature K
U h Heat transfer coefficient kJ/(h m2 K)
V Linear fluid velocity m/h
X i Molar fraction –
Z Reactor length, m M
Greek characters
α W,int Heat transfer coefficient from the bed to the internal wall. W/m2 K
α W,ex Transfer coefficient from the outer shell of the tube to boiling water W/m2 K
∆H Rk Heat of the k-th reaction kJ/g mol
E Fixed bed void fraction –
η Effectiveness factor –
λ rad Effective radial heat conduction in the fixed bed. W/m K
λ wall Thermal conductivity of the reactor wall material W/m K
ρ b Bulk density g/cm3

Appendix 2: Kinetic parameters of the FTS mechanism on co-based catalysts [6].

# Elementary reactions Kinetic parameter Units Energy kJmol−1
Adsorption
1 CO + * ⇆ CO* K 1 = 1.98 × 10−4 MPa−1 ∆H 1 = −48.9
2 H2 + 2* ⇆ 2H* K 2 = 4.92 × 10−4 MPa−1 ∆H 2 = −9.4
Intermediates n  ≥ 3
3DS CO* + C n-1H2n-1* → C n-1H2n-1CO* + * k 3 = 1.24 × 109 mol  g CAT − 1   h − 1 E A3 = 92.8
4 C n-1H2n-1CO* + H* ⇆ C n-1H2n-1CHO* + * K 4 = 1.08 × 106 – ∆H 4 = 16.2
5 C n-1H2n-1CHO* + 2H* ⇆ C n H2n-1* + OH* + * K 5 = 2.94 × 10−1 – ∆H 5 = 11.9
Water formation
6 OH* + H* ⇆ H2O + 2* K 6 = 4.77 × 10−6 MPa ∆H 6 = 14.5
n-paraffin formation n ≥ 3
7DS C n H2n+1* + H* → C n H2n-2 + 2* k 7 = 2.21 × 108 mol  g CAT − 1   h − 1 E A7 = 75.4
1-Olefin formation n  ≥ 3
8DS C n H2n+1* + * → C n H2n  + H* + * k 8 = 1.38 × 108 mol  g CAT − 1   h − 1 E A8 = 92.1

The reaction rate constants for these homologous series are defined by (A2.1):

(A2.1) k i = σ gl , r σ gl , ≠ k B T h exp ( ∆ S i 0 , ≠ ˜ R ) exp ( − ∆ H i 0 , ≠ RT )

Here σ gl,r and σ gl,≠ are the global symmetry number of the reactant and transition state respectively; k B and ℎ are the Boltzman and Planck constants ∆ S i 0 , ≠ ˜ and ∆ H i 0 , ≠ are the entropy and enthalpy of the transition state [34].

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Received: 2024-03-03
Accepted: 2024-10-24
Published Online: 2024-11-21

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Preface of the special issue dedicated to the International Energy Conference (IEC 2023): Energy and Climate Change
  4. Review
  5. Biodegradation of atrazine, a review of its metabolic pathways
  6. Articles
  7. Effect of Ni/tire rubber carbon as catalyst in the hydrodeoxygenation of used vegetable oil: biofuel evaluation in the reduction of atmospheric emissions
  8. Thermochemical energy storage with the solid-gas reaction of SrCO3 improved with CaCO3
  9. Open-loop response of Fischer–Tropsch reactions to manipulation of temperature and pressure
  10. Design and simulation of a full-order robust adaptive observer for monitoring of the biogas process
  11. Comparison of composite metal oxides as oxygen carrier for methane chemical looping reforming
  12. Gas phase carbon dioxide photoreduction to produce value-added chemicals using graphene oxide-based catalysts
  13. Numerical simulation of a chemical looping combustion system using 2D computational fluid dynamics
  14. Hydrogen production by photocatalysis using formic acid and black sand
  15. Carbon dioxide adsorption modeling to determine breakthrough curves in a fixed bed: isotherm and temperature effects
  16. Short Communications
  17. Communication Regarding Articles from the 2023 International Engineering Conference (IEC-2023), held in Zacatecas City, Mexico, from September 18–23, 2023, already published in the International Journal of Chemical Reactor Engineering in 2024
https://doi.org/10.1515/ijcre-2024-0045
Schlagwörter für diesen Artikel
mass and energy balances; Fischer–Tropsch synthesis; open loop response; tubular reactor

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Preface of the special issue dedicated to the International Energy Conference (IEC 2023): Energy and Climate Change
  4. Review
  5. Biodegradation of atrazine, a review of its metabolic pathways
  6. Articles
  7. Effect of Ni/tire rubber carbon as catalyst in the hydrodeoxygenation of used vegetable oil: biofuel evaluation in the reduction of atmospheric emissions
  8. Thermochemical energy storage with the solid-gas reaction of SrCO3 improved with CaCO3
  9. Open-loop response of Fischer–Tropsch reactions to manipulation of temperature and pressure
  10. Design and simulation of a full-order robust adaptive observer for monitoring of the biogas process
  11. Comparison of composite metal oxides as oxygen carrier for methane chemical looping reforming
  12. Gas phase carbon dioxide photoreduction to produce value-added chemicals using graphene oxide-based catalysts
  13. Numerical simulation of a chemical looping combustion system using 2D computational fluid dynamics
  14. Hydrogen production by photocatalysis using formic acid and black sand
  15. Carbon dioxide adsorption modeling to determine breakthrough curves in a fixed bed: isotherm and temperature effects
  16. Short Communications
  17. Communication Regarding Articles from the 2023 International Engineering Conference (IEC-2023), held in Zacatecas City, Mexico, from September 18–23, 2023, already published in the International Journal of Chemical Reactor Engineering in 2024
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