electrochemical production of chemicals
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Electrochemical Production of Chemicals
Narasi Sridhar, Arun Agarwal, and Edward Rode
Applicability to CO2 Conversion
, g ,December 10, 2012
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Industrial scale electrochemistry
Chlor-Alkali production
CO2 related technologiesPresent Industries
Chlor Alkali production
BatteriesCO2 reduction
Desalination, etc.
ThermoelectrofuelsWater electrolysis
PV, fuel cells Electrofuels
Metal extraction
Plating & Polishing
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Electrochemical governing factors
Faraday’s law Faradaic/current efficiency (selectivity)
Polarization Energy consumption
0.7
0.8
0.9
W.h
z.V.alpha=2.02z.V.alpha=4.04z.V.alpha=8.08z V alpha=12 12
Formic acid, 1VSyngas, 1V
Energy efficiency
0.2
0.3
0.4
0.5
0.6
CO
2 C
onve
rted
, ton
s/M
W z.V.alpha=12.12z.V.alpha=16.16
Formic acid, 2VSyngas, 1V
Ethylene, 1V
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Electrochemical Production of Chemicals
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3
0
0.1
0 10 20 30 40 50 60 70 80 90 100
Faradaic Efficiency, Percent
Ethylene, 2VMethane, 2V
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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 (asbestos and non-asbestos) – 3.2 to 3.8 MWh/t Cl2p g ( ) 2
- Membrane - 2.4 to 2.9 MWh/t Cl2
Long history- Over 100 years old- 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
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Technology Advances = Reduce Energy/Increase Efficiency
NAFION® Cation Ion Exchange Membrane Employed
Modular – Skid Mounted Stacks of Single Cells
Optimized Single Cells
Mixed Metal Oxide Based Dimensionally Stable Anodes – long
operating lifeoperating life
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Electrochemical Production of Chemicals
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6 Electrolyzers, 78 cells per stack, Norsk
Hydro, Rafneshttp://www.uhde.eu/fileadmin/documents/brochures/uhde_brochures_pdf_en_10.pdf
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Comparison of Commercial Water ElectrolyzersWater to H2 conversion efficiencies: 80 – 95%Energy Efficiencies (rectifier, electrolyzer, auxiliaries): 56 – 73%H2 purity: 99.8 – 99.998%
Further requirements: Lower electric & capital, higher output pressure, larger sizes
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Electrochemical Production of Chemicals
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National Renewable Energy LaboratoryNREL/FS-560-36705 • September 2004
q p g p p g
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Water electrolyzer capital costs
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NREL report/BK-6A1-46676, 2009
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Capital costs Chlor-alkali plants are capital intensive ($200K/t/d to $1M/t/d)
- Includes auxiliary systems for treating and handling chemicals- Higher temperature (85 to 90 C) requires heating systemsg p ( ) q g y- Extremely corrosive (requiring expensive materials)
Water electrolysis plants to produce hydrogen are less capital intensive depending on sizeon size- Room temperature- Less corrosive (depending on input electrolyte)
CO electrolysis plants may be in-between these two cases CO2 electrolysis plants may be in-between these two cases- We assume similarity to chlor-alkali plants in our analysis
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Electrochemical Production of Chemicals
December 10, 2012 1995 at Institute for Materials Research, Tohoku University
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Pilot Plant of Industrial ScaleHashimoto et al. (2003)
Hydrogen Productionby Seawater Electrolysis
Methane Productionby the reaction ofby Seawater Electrolysis by the reaction of
Carbon Dioxide with Hydrogen4H2O 4H2 + 2O2 CO2 + 4H2 CH4 + 2H2O
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Electrochemical Production of Chemicals
December 10, 2012 2003 at Tohoku Institute of Technology
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From Hashimoto et al.
105
1.14 M NiSO4 + 0.19 M NiCl
2 + 0.49 M H
3BO
3
104m
-2 Ni-Fe-CNi-Fe
Ni-C
3 3 0.108 M FeSO
4 (Fe Source)
0.011 M Lysine (C Source)
103
nsity
/ A
m Fe-CFe
102
rren
t Den
Ni
101
Cur
8 M NaOH at 90°C
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Electrochemical Production of Chemicals
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100
00.10.20.30.40.5Hydrogen Overpotential / V
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100
95Anodically Deposited
at 90°C pH 0 5 600 Am -2ncy
/ %Mn
1-xMo
xO
2+x
Cl2 formation
95 at 90 C, pH 0.5, 600 Amfor 5 min (MnO
2) and 30 min
MnO2n
Effic
ien
902
anode
Evol
utio
n
85
Oxy
gen
E
2
O2 formation
80
O Electrolysis at 1000 Am-2
in 0.5 M NaCl at 30°C
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Electrochemical Production of Chemicals
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0 0.05 0.1 0.15 0.2 0.25Fraction of Mo, x, in Mn
1-xMo
xO
2+x
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CO2 electrochemical conversion – a very brief history Long history of research
- 1970’s – oriented towards local power (U.S. Navy, NASA) - abandoned- 1980’ and early 90’s – fuel production (GRI funded efforts) - abandonedy p ( )- 2000’s – CO2 reduction, renewable power usage orientation
Focused on catalyst development and reaction mechanisms- Only a few full-cell studies- Only a few full cell studies- No engineering/economic requirements established
First engineering/economic study of reactor performance by Oloman and Li (205 –2008)2008)
More complete analyses for formic acid and CO by DNV group (2008 – now)
Other reaction kinetics and scale up studies (e.g., Kenis et al.) p ( g )
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Many electrocatalystsGroup 1 Group 18
1 2
H 1s CO He 1s2
1.0079 Group 2 13 14 15 16 17 4.0026
Group
CO2 Electrocatalysts
H23 4 5 6 7 8 9 10
Li 2s1 Be HC B C N O F Ne6.941 9.012 10.81 12.011 14.0067 15.999 18.998 20.179
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl ArGroup
H2
HCOOH
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 Kr39.098 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 Xe85.468 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 Rn132.905 137.33 138.906 178.49 180.948 183.85 186.207 190.2 192.22 195.08 196.967 200.59 204.383 207.2 208.98 209 210 222
From: Azuma et al., JES, 137 (6), 1772, (1990)-2.2V vs. SCE, 0.05M KHCO3, RT
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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
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Direct CO2 Electrochemical Reduction – Approximate opex
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Trade-offs in Technology DevelopmentRoute Energy
($/ton)Chemicals
($/ton)C.D.
(mA/cm2)1 Alkaline anolyte 393 500 701 Alkaline anolyte 393 500 702 Acidic anolyte 560 3 403 Acidic anolyte – higher productivity
goal560 3 100
20
%)
goal
0
10
1 2 3argi
n (%
Formic Acid = 1,050 $/ton
Capacity = 90,000 ton/year
20 it li ti
-20
-10 1 2 3
Prof
it M 20-year capitalization
No carbon credit
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-30P
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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• Catalyst/Electrode development could increase current to 500 mA/cm2
Alkaline Route Acidic Route
Electrode Current (mA/cm2)
n n
Electrode Current (mA/cm2)
rofit
Mar
gi
500mA/cm2
75%
500mA/cm250%ro
fit M
argi
n100%
75%
% P
r
Stable FE Stable FE25%
500mA/cm2%
Pr
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Technology Development Targets
yHigh Current Density
> 100 mA/cm2Electrode Fab.
True arealif ti
Improved 50%
asib
ility
Long Electrode Life(1 – 2 years)
lifetime(Cathode, Anode)
I it C t l t
mic
Fea High Catalyst Selectivity
(FE > 70%)
Low Energy Consumption
In-situ CatalystReactivation
Eco
nom Low Energy Consumption
(< 10 MWe/ton)
Low Chemical Consumption
Novel Catalysts Selectivity & Reactivity
(Cathode, Anode)
E Low Chemical Consumption
Chemical RoutesReduce corrosivity of chemicals
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y
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Optimal Value Comparison – Acidic and Alkaline Routes
Alkaline70mA/cm2
at 3 25 VmA
/cm
2
Acidic60mA/cm2
at 3.75 V
at 3.25 V
Den
sity
, m Acidic route preferred because ofLower consumables
Cur
rent
Vcell VVcell, V
cy (%
FE)
pH=14 pH=0
ic E
ffici
enc
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20 Vcell, VFara
da
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Multi-Scale Approach
Lab ScaleNovel Cathode &
Sn eletrodepositedcarbon fiber
Macroporous(>80%) Sn sponge
Novel Cathode & Anode catalysts
Reactivity & Selectivity
100m20m 100m20m
50~80 mA/cm2, 70% FE, decrease with time
60~80 mA/cm2, 40% FE, constant over 1day
Bench ScaleContinuous operationContinuous operation
Electrodes, chemistryLifetime
Demo Unit
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Reactor Design
Mass Transfer
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Value Chain AnalysisC id t i ti
Energy
CO2 volume
Economics
Gas with CO2
Energy
CO2 volume
Economics
Gas with CO2
Sensitivity Analysis
Considers uncertainties
Gas sourcedependent
CO2 capture
2from industry
Gas with CO2delivery
gy
Capacities and operational regularities
Gas sourcedependentGas sourcedependent
CO2 capture
2from industry
Gas with CO2delivery
gy
Capacities and operational regularities
Ener
gy
rgy
CO2 capture
CO2 conversion
CO2 delivery
CO2 converted
Ener
g
Ener
gy
rgy
CO2 capture
CO2 conversion
CO2 delivery
CO2 converted
Ener
g
Process Modifications
Ener
gy
Ener
Che
mic
als
Wat
er
CO2 released
Energy
balance
Products
Ener
gy
Ener
Che
mic
als
Wat
er
CO2 released
Energy
balance
Products
Energy2Products
Energy2Products
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Revenue CO2 quotas
Cash flow & NPV
CAPEX, OPEX, Disposal cost, Decommissioning cost Revenue CO2 quotas
Cash flow & NPV
CAPEX, OPEX, Disposal cost, Decommissioning cost
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German Consortia Formed in 2010
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A notional “Integrated CO2 synthesis plant”
Bioreactor
Synthetic FuelSpecialty chemicals
Renewable energy Ancillary services
CO2 ElectroreductionFormate,
formic acid
Source of CO2 Other uses (e.g.)• Fuel cells
OxygenWaste water• Fuel cells• H2 source• Deicing salts• CO source
Fermentation, biogas, air capture
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Summary Electrochemical reduction of CO2 to formic acid or CO appears to be commercially
feasible- Improvements in catalyst stability, current density, and reactor design are necessaryp y y, y, g y
Synthesis of fuels and fine chemicals from CO2 should be considered as a combination of processes much like a refinery or petrochemical complex
M lti l d t ti i i d t i ti d i t f Multi-scale demonstration is a required step in continued improvement of processes- Chlor-alkali industry is still improving after 100+ years!- Economic and sustainability analyses are important
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www.dnv.com
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