3 Narasi Sridhar DNV

Electrochemical Production of Chemicals
Applicability to CO2 Conversion
Narasi Sridhar,, Arun Agarwal,

g , and Edward Rode
December 10, 2012
Industrial scale electrochemistry
Present Industries CO2 related technologies
Chlor-Alkali
Chlor Alkali production
CO2 reduction
Batteries
Water electrolysis
Thermoelectrofuels
Desalination, etc.
PV, fuel cells Electrofuels
Metal extraction
Plating & Polishing

December 10, 2012
© Det Norske Veritas AS. All rights reserved. 2
Electrochemical governing factors
Faraday’s law Faradaic/current efficiency (selectivity)
Polarization Energy consumption
0.9
z.V.alpha=2.02
0.8 Formic acid, 1V
z.V.alpha=4.04
Syngas, 1V
z.V.alpha=8.08
W.h
0.7
z V alpha=12 12
z.V.alpha=12.12
CO2 Converted, tons/MW
Energy efficiency 0.6
0.5
z.V.alpha=16.16
0.4 Formic acid, 2V

Syngas, 1V
0.3
0.2 Ethylene, 1V
Ethylene, 2V
0.1
Methane, 2V
0
0 10 20 30 40 50 60 70 80 90 100
Faradaic Efficiency, Percent
December 10, 2012
The Chlor Alkali Process
 Three electrochemical processes (numbers from J. Appl. Elect., 2008)
- Mercury (being phased out) – 3.1 to 3.4 MWh/t Cl2
- Diaphragm
p g ((asbestos and non-asbestos)) – 3.2 to 3.8 MWh/t Cl2
- Membrane - 2.4 to 2.9 MWh/t Cl2
 Long history
- Over 100 years old
- Energy reduction innovations occur even today (e.g., Oxygen depolarization cathodes)
- Initial concept of ODC in 1950, but developments continued through 2000’s.
- Large surface area (>2 m2 ) and long life times possible (>3 years)
- But energy reduction must consider other factors

December 10, 2012
Technology Advances = Reduce Energy/Increase Efficiency
NAFION® Cation Ion Exchange Optimized Modular – Skid Mounted
Membrane Employed Single Cells Stacks of Single Cells
Mixed Metal Oxide Based

Dimensionally Stable Anodes – long
operating life
6 Electrolyzers,
78 cells per
http://www.uhde.eu/fileadmin/documents/brochures/uhde_brochures_pdf_en_10.pdf
December 10, 2012 stack, Norsk
© Det Norske Veritas AS. All rights reserved.
Hydro, Rafnes
Comparison of Commercial Water Electrolyzers
Water to H2 conversion efficiencies: 80 – 95%
Energy Efficiencies (rectifier, electrolyzer, auxiliaries): 56 – 73%
H2 purity: 99.8 – 99.998%
Further requirements:
q Lower electric & capital,
p higher
g output
p p pressure, larger
g sizes
Electrochemical Production of Chemicals National Renewable Energy Laboratory

December 10, 2012 NREL/FS-560-36705 • September 2004
Water electrolyzer capital costs
NREL report/BK-6A1-46676, 2009

December 10, 2012
Capital costs
 Chlor-alkali plants are capital intensive ($200K/t/d to $1M/t/d)
- Includes auxiliary systems for treating and handling chemicals
- Higher
g temperature
p ((85 to 90 C)) requires
q heating
g systems
y
- Extremely corrosive (requiring expensive materials)
 Water electrolysis plants to produce hydrogen are less capital intensive depending
on size
- Room temperature
- Less corrosive (depending on input electrolyte)
 CO2 electrolysis plants may be in-between these two cases

- We assume similarity to chlor-alkali plants in our analysis

December 10, 2012
December 10, 2012
1995 at Institute for Materials Research, Tohoku University
Pilot Plant of Industrial Scale
Hashimoto et al. (2003)
Hydrogen Production Methane Production

by Seawater Electrolysis by the reaction of
Carbon Dioxide with Hydrogen
4H2O  4H2 + 2O2 CO2 + 4H2  CH4 + 2H2O

December 10, 2012
© Det Norske Veritas AS. All rights reserved. 2003 at Tohoku Institute of Technology
From Hashimoto et al.
105
1.14 M NiSO4 + 0.19 M NiCl2
+ 0.49 M H3BO3
0.108 M FeSO4 (Fe Source)
104 0.011 M Lysine (C Source)
Ni-Fe
m-2
Ni-C Ni-Fe-C
nsity / Am
Fe-C
103 Fe
Currrent Den
102
Ni
101
8 M NaOH at 90°C
100
Electrochemical Production of Chemicals 0.5 0.4 0.3 0.2 0.1 0
December 10, 2012
© Det Norske Veritas AS. All rights reserved. Hydrogen Overpotential / V
100
Evolutionn Efficienncy / % Mn1-xMoxO2+x
Cl2 formation Anodically Deposited
95 at 90
90°C 5 600 Am -2
C, pH 00.5,
for 5 min (MnO 2) and 30 min
MnO2
90 anode
Oxygen E
85 O2 formation
O
Electrolysis at 1000 Am -22

in 0.5 M NaCl at 30°C
80
0 0.05 0.1 0.15 0.2 0.25
Electrochemical Production of Chemicals Fraction of Mo, x, in Mn 1-xMoxO2+x
December 10, 2012
CO2 electrochemical conversion – a very brief history
 Long history of research
- 1970’s – oriented towards local power (U.S. Navy, NASA) - abandoned
- 1980’ and earlyy 90’s – fuel p
production ((GRI funded efforts)) - abandoned
- 2000’s – CO2 reduction, renewable power usage orientation
 Focused on catalyst development and reaction mechanisms

- Only a few full-cell
full cell studies
- No engineering/economic requirements established
 First engineering/economic study of reactor performance by Oloman and Li (205 –

2008)
 More complete analyses for formic acid and CO by DNV group (2008 – now)
 Other reaction kinetics and scale up
p studies ((e.g.,
g Kenis et al.))

December 10, 2012
Many electrocatalysts
Group 1 CO2 Electrocatalysts Group 18
1 2
H 1s CO Group He 1s 2
1.0079 Group 2 13 14 15 16 17 4.0026

3 4
H2 5 6 7 8 9 10
Li 2s
1
Be HC B C N O F Ne
6.941 9.012 10.81 12.011 14.0067 15.999 18.998 20.179
11 12
HCOOH 13 14 15 16 17 18
Na Mg Group Al Si P S Cl Ar
22.989 24.305 3 4 5 6 7 8 9 10 11 12 26.982 28.086 30.974 32.06 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.098 40.08 44.956 47.88 50.942 51.996 54.938 55.847 58.933 58.69 65.39 69.72 72.59 74.922 78.96 79.904 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.468 87.62 88.906 91.224 92.906 95.94 98 101.07 102.906 106.42 107.868 112.41 114.82 118.71 121.75 127.6 126.905 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905 137.33 138.906 178.49 180.948 183.85 186.207 190.2 192.22 195.08 196.967 200.59 204.383 207.2 208.98 209 210 222
From: Azuma et al., JES, 137 (6), 1772, (1990)

-2.2V vs. SCE, 0.05M KHCO3, RT

December 10, 2012
Thermodynamics of CO2 reduction
Thermodynamically, reduction of
CO2 should be as feasible as that
of water
Practically, CO2 reduction is

governed by:
g y
• Low kinetics
• Product economics

December 10, 2012
Direct CO2 Electrochemical Reduction – Approximate opex

December 10, 2012
Trade-offs in Technology Development
Route Energy Chemicals C.D.
($/ton) ($/ton) (mA/cm2)
1 Alkaline anolyte 393 500 70
2 Acidic anolyte 560 3 40
3 Acidic anolyte – higher productivity 560 3 100
goal
20
%)
Profit Margin (%
10 Formic Acid = 1,050 $/ton

0 Capacity = 90,000 ton/year
1 2 3 20
20-year capitalization
it li ti
-10
No carbon credit
-20
P
-30
December 10, 2012
Profit Margin - CAPEX and OPEX
• Alkaline route requires high current density and FE for profitability

• Acid route requires lower current density and lower stable FE
• Catalyst/Electrode development could increase current to 500 mA/cm2
Alkaline Route Acidic Route

Electrode Current (mA/cm2) Electrode Current (mA/cm2)
% Prrofit Margin
% Prrofit Margin
n
75%
500mA/cm2 50%
500mA/cm2
100%
75% Stable FE 25% Stable FE

December 10, 2012
Technology Development Targets
Improved High Current Density Electrode Fab.
50% > 100 mA/cm2 True area
asibilityy
lif ti
lifetime
Long Electrode Life (Cathode, Anode)
(1 – 2 years)
mic Fea
High Catalyst Selectivity IIn-situ

it Catalyst
C t l t
(FE > 70%) Reactivation
Econom
Low Energy Consumption

(< 10 MWe/ton) Novel Catalysts
Selectivity & Reactivity
(Cathode, Anode)
Low Chemical Consumption
E
Reduce corrosivityy of chemicals Chemical Routes
Electrochemical Production of Chemicals 19

December 10, 2012
Optimal Value Comparison – Acidic and Alkaline Routes
2
Alkaline
Current Density, mA/cm
70mA/cm2
m
at 3
3.25
25 V
Acidic route preferred because of
Acidic
Lower consumables
60mA/cm2
at 3.75 V
Vcell V
Vcell,
Faradaic Efficienccy (%FE)
pH=14 pH=0

December 10, 2012
Vcell, V
Multi-Scale Approach
Lab Scale Macroporous

(>80%) Sn sponge
Sn eletrodeposited
carbon fiber
Novel Cathode &

Anode catalysts
Reactivity & 20m 100m
Selectivity 60~80 mA/cm2, 40% FE,

constant over 1day
50~80 mA/cm2, 70% FE,
decrease with time
Bench Scale
Continuous operation
Electrodes, chemistry
Lifetime
Demo Unit
Reactor Design
December 10, 2012 Mass Transfer
Value Chain Analysis
C id
Considers t i ti
uncertainties
Energy
CO2 volume
Sensitivity Analysis
Economics
Gas with CO2

from industry
Capacities and operational regularities
Gas with CO2
Gas source delivery
dependent
gy
CO2 capture
Energ
Energy
CO2 delivery
Process
Modifications
Enerrgy
CO2 conversion CO2 converted
Energy
Chemicals
Energy
balance
Water
CO2 released
Products
Energy
CAPEX, OPEX, Disposal cost, Decommissioning cost Revenue CO2 quotas

December 10, 2012
© Det Norske Veritas AS. All rights reserved. Cash flow & NPV 22
German Consortia Formed in 2010

December 10, 2012
A notional “Integrated CO2 synthesis plant”
Specialty chemicals Synthetic Fuel
Bioreactor
Renewable energy Ancillary services
Formate,
CO2 Electroreduction formic acid
Source of CO2 Waste water Oxygen Other uses (e.g.)

• Fuel cells
• H2 source
Fermentation, biogas, • Deicing salts
air capture • CO source

December 10, 2012
Summary
 Electrochemical reduction of CO2 to formic acid or CO appears to be commercially
feasible
- Improvements
p in catalyst
y stability,
y, current density,
y, and reactor design
g are necessaryy
 Synthesis of fuels and fine chemicals from CO2 should be considered as a

combination of processes much like a refinery or petrochemical complex
 Multi-scale
M lti l demonstration
d t ti is i a required
i d step
t iin continued
ti d iimprovementt off processes
- Chlor-alkali industry is still improving after 100+ years!
- Economic and sustainability analyses are important

December 10, 2012
Safeguarding life, property
andd the
th environment
i t
www.dnv.com

December 10, 2012

3 Narasi Sridhar DNV

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Electrochemical Production of Chemicals

Applicability to CO2 Conversion

Narasi Sridhar,, Arun Agarwal,

PV, fuel cells Electrofuels

Plating & Polishing

Electrochemical Production of Chemicals

Faraday’s law Faradaic/current efficiency (selectivity)

Polarization Energy consumption

Energy efficiency 0.6

0.4 Formic acid, 2V

Electrochemical Production of Chemicals

Mixed Metal Oxide Based

Electrochemical Production of Chemicals National Renewable Energy Laboratory

NREL report/BK-6A1-46676, 2009

 CO2 electrolysis plants may be in-between these two cases

Electrochemical Production of Chemicals

Hydrogen Production Methane Production

Electrochemical Production of Chemicals

Electrolysis at 1000 Am -22

 Focused on catalyst development and reaction mechanisms

 First engineering/economic study of reactor performance by Oloman and Li (205 –

Electrochemical Production of Chemicals

1.0079 Group 2 13 14 15 16 17 4.0026

From: Azuma et al., JES, 137 (6), 1772, (1990)

Electrochemical Production of Chemicals

Practically, CO2 reduction is

Electrochemical Production of Chemicals

Electrochemical Production of Chemicals

10 Formic Acid = 1,050 $/ton

• Alkaline route requires high current density and FE for profitability

Alkaline Route Acidic Route

75% Stable FE 25% Stable FE

Electrochemical Production of Chemicals

High Catalyst Selectivity IIn-situ

Low Energy Consumption

Reduce corrosivityy of chemicals Chemical Routes

Electrochemical Production of Chemicals 19

Electrochemical Production of Chemicals

Lab Scale Macroporous

Novel Cathode &

Selectivity 60~80 mA/cm2, 40% FE,

Gas with CO2

CO2 conversion CO2 converted

CAPEX, OPEX, Disposal cost, Decommissioning cost Revenue CO2 quotas

Electrochemical Production of Chemicals

Electrochemical Production of Chemicals

Renewable energy Ancillary services

Source of CO2 Waste water Oxygen Other uses (e.g.)

Electrochemical Production of Chemicals

 Synthesis of fuels and fine chemicals from CO2 should be considered as a

Electrochemical Production of Chemicals

Electrochemical Production of Chemicals

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