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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2021, Vol. 15 Issue (1) : 208-219    https://doi.org/10.1007/s11705-020-1945-6
RESEARCH ARTICLE
Electrolytic cell engineering and device optimization for electrosynthesis of e-biofuels via co-valorisation of bio-feedstocks and captured CO2
Faraz Montazersadgh1, Hao Zhang1, Anas Alkayal2, Benjamin Buckley2, Ben W. Kolosz3, Bing Xu4, Jin Xuan1()
1. Department of Chemical Engineering, Loughborough University, Loughborough, LE11 3TU, UK
2. Department of Chemistry, Loughborough University, Loughborough, LE11 3TU, UK
3. Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, MA 01609-2280, USA
4. Department of Accountancy, Economics and Finance, Heriot-Watt University, Edinburgh, EH14 4AS, UK
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Abstract

Utilizing CO2 in an electro-chemical process and synthesizing value-added chemicals are amongst the few viable and scalable pathways in carbon capture and utilization technologies. CO2 electro-reduction is also counted as one of the main options entailing less fossil fuel consumption and as a future electrical energy storage strategy. The current study aims at developing a new electrochemical platform to produce low-carbon e-biofuel through multifunctional electrosynthesis and integrated co-valorisation of biomass feedstocks with captured CO2. In this approach, CO2 is reduced at the cathode to produce drop-in fuels (e.g., methanol) while value-added chemicals (e.g., selective oxidation of alcohols, aldehydes, carboxylic acids and amines/amides) are produced at the anode. In this work, a numerical model of a continuous-flow design considering various anodic and cathodic reactions was built to determine the most techno-economically feasible configurations from the aspects of energy efficiency, environment impact and economical values. The reactor design was then optimized via parametric analysis.
Keywords electrosynthesis      e-biofuels      CO2 utilization      computational model     
Corresponding Author(s): Jin Xuan   
Online First Date: 13 July 2020    Issue Date: 12 January 2021
 Cite this article:   
Faraz Montazersadgh,Hao Zhang,Anas Alkayal, et al. Electrolytic cell engineering and device optimization for electrosynthesis of e-biofuels via co-valorisation of bio-feedstocks and captured CO2[J]. Front. Chem. Sci. Eng., 2021, 15(1): 208-219.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1945-6
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I1/208
Reaction No. Reaction Conditions Ref.
1 4OH?→ O2 + 2H2O+ 4e? Pt, 1 mol/L, 6°C±1°C [16]
2 HCOO?→ CO2 + H+ + 2e? Pd, 1 mol/L, 6°C±1°C [16]
3 2 CH3COO?→ CH3CH3 + 2CO2 + 2e? 1 mol/L, pH>4, 348 K [17,18]
4 2propionate?→ C4H10 + 2CO2 + 2e? Pt, 1 mol/L, pH= 7 [17,19]
5 methanol+ 2H2O → HCO3? + 7H+ + 6e? pH= 7 [19]
6 ethanol+ 5H2O → 2HCO3? + 14H+ + 12e? pH= 7 [19]
7 C3H8O3 + 8OH-→ 3HCOOH+ 5H2O+ 8e- 298 K, 1 bar [20]
8 C3H8O3 + 2OH-→ C3H6O3 + 2H2O+ 2e- 298 K, 1 bar [20]
9 Ph–CH?OH–CH3→ Ph–C=O–CH3 + 2e- + 2H+ 0.2 mmol/L TEMPO, 0.5 mol/L NAHCO3 [21]
10 + 6OH-→ + 4H2O+ 6e- Pt, 0.3 mol/L NaClO4, pH= 10 to 13, 20°C [22,23]
11 + 4OH-→ + 2H2O+ 4e- pH<7.0, NiFe LDH [24]
12 →+ CO2 + 4H+ + 4e- AgO, NaOH [25]
13 C6H12O6 + 2OH-→ C6H12O7 + H2O+ 2e- 298 K, 1 bar [20]
14 CH4 + 2OH-→ CH3OH+ H2O+ 2e- 298 K, 1 bar [20]
15 → +2e? + 2H+ KI, H2O, t-BuOH [26]
Tab.1  Anodic reactions with water as solvent
Reaction No. Reaction Conditions Ref.
16 + MeOH → + 2e- + 2H+ 10°C?15°C [29]
17 + MeOH → + 2H+ + 2e? ET3N-3HF, Pt [26]
18 + MeOH → +H+ + e? KOH [30]
19 +H2O → + H+ + e? MeCN [31]
20 + CN?→ + e? 298 K, 1 bar [32]
Tab.2  Anodic reactions with DMF as solventa)
Reaction No. Reaction Conditions Ref.
21 CO2 + H2O+ 2e?→ HCOO? + OH? 298 K, 1 bar [33]
22 2?CO2 + 2?H+?+ 2?e-→ 298 K, 1 bar [33]
23 CO2 + 2?H+?+ 2?e-→ HCOOH 298 K, 1 bar [33]
24 CO2 + 2?H+?+ 2?e-→ CO+ H2O 298 K, 1 bar [33]
25 CH3OH+ 2?H+?+ 2?e-→ CH4(g) +?H2O 298 K, 1 bar [33]
26 O2 + 4?H+?+ 4?e-→ 2H2O 298 K, 1 bar [33]
27 SO2 + 4?H+?+ 4?e-→ S(s) + 2H2O 298 K, 1 bar [33]
28 MnO4-?+ 8?H+?+ 5?e-→ Mn2+?+ 4H2O 298 K, 1 bar [33]
29 Fe2O3(s) + 3H2O?+ 2?e-→ 2Fe(OH)2(s) + 2OH- 1 mol/L, 1 bar, 80°C [34]
30a) + 2?H+?+ 2?e?→ 298 K, 1 bar [33]
Tab.3  Cathodic reactions with organic and inorganic solvent
Fig.1  Model schematic for e-biofuel reactor.
Fig.2  (a) Velocity field of the gas and liquid (m/s); (b) dimensionless velocity profile across channel height at 6 mm from the entrance, model results vs. experimental measurements [42].
Quantity/unit Value
Electrolyte conductivity /(S?m?1) 0.4
Channel height /mm 1.5
Channel length /mm 15
Flow velocity /(m?s?1) 0.005
Electrolyte Density /(kg?m?3) 1008
CO2 initial concentration /(mol?L?1) 0.001
Cathode equilibrium potential /V ?1.02
Cathode HER equilibrium potential /V ?0.83
Anode equilibrium potential /V 0
Cathode exchange current density /(A?m?2) 0.1
Cathode HER exchange current density /(A?m?2) 0.016
Anode exchange current density /(A?m?2) 0.02
OH? initial concentration /(mol?L?1) 1e?4
Electrolyte flow rate /(L?min?1) 0.5e?3
V polarization /V 1.5
Anode charge transfer coefficient 0.16
Cathode charge transfer coefficient ?0.05
Cathode HER charge transfer coefficient ?0.5
Channel depth /cm 0.5
Porous height /mm 0.3
Gas channel height /mm 1
Electrode permeability /m2 1e?12
Electrode porosity 0.7
Gas density /(kg?m?3) 1.562
Gas viscosity /(kg?m?1?s?1) 1.48e?5
Tab.4  Model input parameters
Fig.3  Model results vs. experimental data for pH= 10.0 [43].
Reaction number Limiting factor
1, 21, 25, 27 electrode diffusivity
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 anodic reaction
16, 17, 18, 19, 20, 22, 23, 24 cathodic reaction, CO2
26, 28, 29, 30 cathodic reaction
Tab.5  Cell kinetics limiting factor according to the chosen cell kinetics scheme
Fig.4  (a) Energy efficiency and (b) current efficiency for various half-cell reactions.
Fig.5  (a) CO2 removal rate and (b) E-factor for various half-cell reactions.
Fig.6  Product added value.
Fig.7  Cell design optimization parameters. (a) Channel length vs. energy conversion rate, (b) electrolyte flowrate vs. CO2 conversion rate, (c) CO2 inlet flowrate vs. CO2 conversion rate and (d) channel height vs. energy conversion rate.
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