NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Benefits and Hurdles for Biological Methane Upgrading

Fei, Qiang

Sustainable Chemicals & Plastics Adoption & Applications Summit

San Diego, California September 1-3, 2015

NREL/PR-5100-64878

2

Energy Extraction (natural gas and

petroleum) 29%

Agriculture (enteric fermentation)

25%

Waste Management (landfills)

18%

Coal Mining 10%

Manure Management

9%

Others 9%

U.S. Methane emissions by sources from 1990-2012 (US_EPA 2015)

Methane Source Most energy dense alkane: 55 MJ/kg Extraction: Natural gas (90% CH4) Anaerobic digestion: Biogas (60% CH4) Global-warming potential (GWP) of CH4 :

CH4 lifetime is 12 years 100-year GWP: 21 times of CO2 20-year GWP: 72 times of CO2

Methane Cost Natural gas: pipeline NG vs. industrial waste

stream (flaring gas) Biogas: associates with plant size

Source: U.S. Energy Information Administration.

0%

10%

20%

30%

40%

50%

0

2

4

6

8

10

1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012

Shal

e G

as W

ithdr

awal

s in

Tota

l US

Nat

ural

Gas

With

draw

als (

%)

U.S

. Nat

ural

Gas

Wel

lhea

d Pr

ice

(Dol

lars

per

Tho

usan

d ft

3 )

U.S. Natural Gas Wellhead Price (Dollars per Thousand Cubic Feet)Shale Gas Withdrawals in Total US Natural Gas Withdrawals (%)

Biogas source $/MMBTU

Reference

Landfill 2-4 California Energy Commission, 2012

Livestock manure 6-10 CALSTART, 2010

Wastewater treatment plants 2-8 Nicholas Institute report,2014

Biomass 6-8 Nicholas Institute report,2014

Dairy farm 11 NRRL report, 2010

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Methane Production and Use in the US Methane production

Natural gas: 65.9 billion Bcf/d

Biogas: 1.79 billion Bcf/d

Natural gas & Biogas

Bioprocess (Fermentation)

Chemical, Nutrient,

& Fuel

NG use Biogas use

Bioconversion of NG/Biogas

Natural gas production map

Biogas production map

Methane use Boiler: 85% heat and 15% lost

Combined heat and power (CHP): 50% heat, 35% electricity and 15% lost

1m3 biogas=2 kWh (35% ECE)

Upgrading (chemical and biological): chemical, nutrient and transportation fuel

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Rule of Methane Production and Use Regulation

Methane availability: Control and Storage Technology demand: Conversion Process Product: Bio-base Fuel and Chemical Player: EPA, USDA, DOE, American Biogas Council, DOD,

State government, North Dakota Industrial Commission (NDIC), etc.

Rule: Renewable Fuel Standard II, Low Carbon Fuel Standard, 2007 Energy Bill, Farm Bill, Treasury Grants, Clean Air Act, Climate Action Plan, etc.

Source: North Dakota Petroleum Council

Renewable Chemical

Biofuel

Sustainable product

Methane production and storage

Novel biological

conversion process

Bio-based products

Methanotroph

Gas Fermentation

Natural Gas

Biogas

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Biological Conversion of Methane

Methanotrophic bacteria (Aerobic cultivation)

Product Formula Application

Fomate CH2O2 Chemical

Glycogen C6H12O6 Chemical

Ectoine C6H10N2O2 Healthy care

Astaxanthin C40H52O4 Healthy care

Sucrose C12H22O11 Chemical

Isoprene C5H8 Fuel/Rubber

Lactic acid C3H6O3 Chemical

Lipid C15-C18 Fuel

PHB C4H8O2 Fuel/plastic

Single cell protein* Nutrient

*, including glutamic acid, aspartic acid, alanine, leucine, valine, glycine, lysine, isoleucine, threonine, serine etc.

Intracellular Products

Extracellular Products

Selected products

Source: Conrado & Gonzalez, 2014. Science, 343: 621/Haynes & Gonzalez, 2014. Nat. Chem. Biol. 10: 331

Biological routes chemical route for fuel

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Hurdles of Bioconversion of Methane Safety consideration Limiting Oxygen Concentration (LOC) = 12 vol % O2 UEL of CH4: 15% in Air (v/v) LEL of CH4: 5% in Air (v/v)

Source: wikipedia.com

CH4 Flammability Diagram

Source: Extremophilic Bioprocessing of Lignocellulosic Feedstocks to Biofuels, Value-Added Products, and Usable Power. Chapter: Bioconversion of Methane for Value Added Products

NREL lab-scale continuous gas delivery system

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Hurdles of Bioconversion of Methane

Methane Collection

Gas Fermentation

Strain Modification

Methanotroph Screening

Bioreactor Design

Bioprocess Development

Biomass & Product

Collection

Product Separation

Optimization of Culture Condition

Oxygen Supply

Waste Water Treatment

Product Upgrading

Upgrading Development

Desired Product

Byproduct Packaging,

Transportation and Marketing

Gas Cleaning

Technical hurdles (R&D Map for Bioconversion of Methane ) Gas Supply & Cleaning Bioprocess Development Product Separation & Upgrading

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Hurdles of Bioconversion of Methane Gas Supply & Cleaning

Flow rate: Plant capacity and productivity Biogas: 20-11000 (1000m3/hr) Natural gas:

Location: transportation and water availability Impurity and cleaning method:

Natural gas vs. Biogas CO2, H2S, higher chain hydrocarbons (in NG)

Oxygen supply: Pure oxygen costs as mush as methane on final product price Gas cleaning: Adsorption (PSA) vs. Membrane vs. Absorption vs. Cryogenic

Bioprocess Development Strain modification: carbon conversion efficiency, growth rate, pathway modification Culture condition: pH, T, Cu2+, CH4/O2 ratio, pO2, Bioreactor design (gas transfer efficiency): CSTR/micro-bubble, loop/air-lift, bubble

column, trickle-bed, membrane-based, nanoparticles gas substrate carrier

Product Separation and Upgrading Intercellular product (single cell protein, lipid/fatty acid, PHB): S/L separation,

extraction, and upgrading Extracellular product (lactic acid, butanol, isoprene): purification, extraction

(harvesting), and upgrading

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Bioconversion of Methane at NREL Methane source: Natural gas and Biogas Product: Lipid, Carbohydrate, Lactic acid & Muconic acid Bioprocess:

Safety control system Strain screening with continuous gas delivery Seed train development Batch production culture with continuous gas delivery High cell density culture: Dry cell density up to 20 g/L Scale up of fermentation: 50 mL to 5L

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Techno-economic Analysis at NREL

-35%

-30%

-25%

-20%

-15%

-10% -5

% 0% 5% 10%

15%

20%

25%

30%

A400: H2, $/ton (1147:1835:3211)

A200: Ca(OH)2 cost, (50:102:150)

A400: Upgrading catalyst cost, % OPEX (1:5:10)

A300: Flocculant usage, mg/L (1:15:50)

A300: FA extraction yield, g FA/g extractable lipid (88%:80%:70%)

A100: Natural gas, $/MM BTU (2.5:4.0:7.0)

A400: Diesel conversion efficiency, g diesel/g fatty acid…

A200: Nitrogen source, $/ton (187:560:1246)

A200: CCE, FA C mol/ CH4 C mol (30%:20%:10%)

A200: Fatty acid productivity, g/L/h (0.92:0.5:0.1)

A200: Fatty acid content, g fatty acid/g cell mass (30%:20%:15%)

Diesel fuel Base Price

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Acknowledgements NREL

• Philip T. Pienkos • Nancy Dowe • Mike Guarnieri • Ling Tao • Holly Smith

University of Washington • Mary Lidstrom • Marina Kalyuzhnaya

Lanza Tech • Derek Griffin • Ignasi Palou-Rivera

NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Thank you for your time

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