Utilization of Gaseous Carbon Waste Streams

NAS, NAE, NAM Board on Chemical Sciences and TechnologyUtilization of Gaseous Carbon Waste Streams Webinar III

28 March 2018

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Baseline scenarios of CO2 emissions per year out to 2100. All 2° C scenarios require net negative CO2 emissions by ~ 2080.

ExxonMobil Outlook for Energy 2018: A view to 2040

Gig

aton

nes

emitt

ed C

O2/y

ear A more probable scenarios

cumulative emissions ~ 5000 GtCO2 by 2100

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IPCC Climate Change 2014 Synthesis Report

😢😢Likely scenarios have carbon emission

continuing well past 2100

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Crops capture 30 GtCO2 /year. Pasture: 48 GtCO2Total Global human emissions in 2015 =32 GtCO2

Source: The Methanol Economy, Alain Goeppert, Miklos Czaun, John-Paul Jones, Surya Prakash, George Olah Chem Soc Rev., DOI: 10.1039/c4cs00122b (2014)

• Reforestation

• Conversion of agricultural residues to chemicals, fuels and other useful products

• Capture and sequestration of excess CO2

• If we are to continue to use natural gas (CH4), we have to convert it to H2 and CO2 and sequester CO2.

Global greenhouse gas emissions by sector for 2005

Global CO2 emissions from cement production

Source: R.M. Andrew, Earth Syst. Sci. Data, 10, 195–217, 2018 https://doi.org/10.5194/essd-10-195-2018

CO2 cement emissions from

China 1980–2016

CO2 cement emissions from India, USA, Turkey,

Vietnam

Source: R.M. Andrew, Earth Syst. Sci. Data, 10, 195–217, 2018 https://doi.org/10.5194/essd-10-195-2018

SEAB Task Force Report on CO2 Utilization and Negative emissions Technologies

https://energy.gov/sites/prod/files/2016/12/f34/SEAB-CO2-TaskForce-FINAL-with%20transmittal%20ltr.pdf

The largest emitters of CO2 (in 2005)

1. Transportation fuels (15% of CO2 emissions)

2. Cement (5%)

3. Chemicals & plastics (4.1%)

4. Iron and steel (4%)

The utilization of captured carbon should focus on the major uses of carbon

“Sky” Scenario of how to transition to net zero emissions by 2070 and negative

carbon emissions by 2100

Source: https://www.shell.com/energy-and-innovation/the-energy-future/scenarios/shell-scenario-sky.html

Paris Agreement: Limit global average temperature to well below 2°C above pre-industrial levels; Pursue efforts to limit the temperature increase to 1.5°C above pre-industrial levels.

SHELL “Sky Scenario” to meet the Goals of the Paris Agreement (2018)

Source “Sky SHELL Scenarios Meeting the Goals of the Paris (2018)”

In Sky, passenger electric vehicles reach cost parity with combustion engine cars by 2025. By 2035, 100% of new car sales are electric in the

EU, US, and China, with other countries and regions close behind.

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100% renewable energy will require recycling combustion products

Electrochemical

Biochemical

Thermochemical

Photochemical

CO2

H2O

Liquid hydro-carbonH2, CO

H2 , O2

A challenge for the 21st Century

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How much does it cost to ship and store oil any where in the world?

2 ₵ /gallon of gasoline.

Oil tankers are transcontinental energy “transmission lines”

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Unsubsidized cost of tenewable energy costs (L.C.O.E.) at an increasing number of sites

around the world are < 3 ¢/kWh.

Costs at the best sites are expected to be~ 2 ¢/kWh by 2030

17Source: https://www.lazard.com/perspective/levelized-cost-of-energy-2017/

L.C.O.E of nuclear, coal, gas-combined cycle, utility scale solar and wind energy

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UK National Grid Electricity Costs

Onshore wind

Offshore wind

Natural gas

Wholesale price

2017 bid: £58 / MWh

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Clean electricity at 2 – 3 ¢/kWh opens up exciting opportunities

in electrochemistry

Large scale commercial electrochemical production of H2, O2 and CO may become a reality

Thermodynamics & Cost LimitsH20 = H2 + ½ O2 ; ΔG = 237.2 kJ/mol = 32.4 kWh/kg-

H2

$/kg-H2

Carbon-free Energy Cost ($/MWh)

Thermodynamic limit

• Artificial Alveolus for Efficient electrochemistry,• Artificial Alveolus for Highly Efficient Oxygen Reduction and Evolution

Jun Li … Steven Chu and Yi Cui (submitted)

Jun LiYi Cui

(HER) Reduction at cathode: 4 H+(aq) + 4e− → 2 H2(g)

(OER) Oxidation at anode: 2 H2O(l) → O2(g) + 4 H+(aq) + 4e−

2 H2O(l) → O2(g) + 2 H2(g)

Electrolysis of water

catalyst

hydrophobic polyethylene

- 1 atm

Hydrogen evolution reaction

The membrane (alveolus) structure shows 5x higher than the same catalyst using a solid electrode.

Comparison of catalyst performance on a alv-PE membrane with a flat membrane

Oxygen evolution reaction

Catalyst on metal electrode

alv-structure

Cathode: 4 H+(aq) + 4e− → 2 H2(g)

Anode: 2H2O(l) → O2(g) + 4 H+(aq) + 4e−

O2 H2

H2O in

O2

H2

O2

H2

10s of meter

s

Spacing~100 μm ?

A major cost barrier of electrochemical production is the physical size of the chemical plants. Separators keep OER and HER

electrodes from touching. The small gaps begin to approximate 3-D electrolysis

CO2 reduction

Equilibrium potential of -0.11 V (vs RHE) for CO2/CO• Lowest onset potentials of -0.27 V vs. RHE (160 mV overpotential for

CO2/CO). Peak FECO value of ~ 92% at -0.6 V vs. RHE

Conversion rate has to be increases by at least 10x and energy efficiency at higher current decreases due to resistive losses.

Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials, Richard Masel, et al. ,Science 334, 643 -644 (2011) DOI: 10.1126/science.1209786

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The Methanol EconomyAlain Goeppert, Miklos Czaun, John-Paul Jones, Surya Prakash, George Olah

Chem Soc Rev., DOI: 10.1039/c4cs00122b (2014)

H2 from electrolysis of water or the gasification of biomass plus CO2 to be used to produce methanol or DME.

• Brazilian sugarcane ethanol• Biomass Pyrolysis for Advanced

Biofuels• Cellulosic Biofuels• Synthetic Biology Production

from CO2• Lipid-Based Biodiesels

• Electro-fuels

• Biochar Carbon Sequestration

Is it possible to use engineered microbes to convert hydrogen and CO2 into ethanol, butanol of

other fuels?

If H2 is used as a feedstock, then low cost clean energy-based electrolysis avoids the “catch-radius” problems of cellulosic-based bio-fuels since clean

electricity can be easily transported over long distances

One potential new version of an electro-fuel

The utilization of captured carbon for cement materials is another application. The application of carbon-fiber based materials to date is

limited to high-strength/weight demands such as airplanes. The use of wood as a structural material is a form of CO2 capture and

sequestration.

“Processing bulk natural wood into a high-performance structural material”, Jianwei Song, et al. Nature 554, 254 (2018)

Processing bulk natural wood into a high-performance structural material, Jianwei Song, et al. Nature 554, 254 (2018)

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