CO2 CH4

Methane Hydrates: CO2 storage and natural gas production

Source: IPCC (2007): Climate Change - Mitigation

Hydrate technologies may contribute to the reduction of CO2 emissions from fossil fuel power plants

Global Methane Hydrate Distribution

0 200 500 kg C/m2

Source: Modeling study by Burwicz, Rüpke & Wallmann (GCA, 2011)

Hydrates formed by microbial methane production within the GHSZ: 990 Gt C

Global Methane Hydrate Distribution

Hydrates formed by microbial methane production and upward fluid flow: 3500 Gt C

Wallmann, Pinero et al. (2011)

Global Methane Hydrate Inventory in the Seabed

Kven. (1999)

Mil. (2004)

Buff. (2004)

Klau. (2005)

Best estimate 3000 2000

Gt C

Global Methane Hydrate Inventory

Coal Oil Gas Hydrate

Source: Energy Outlook 2007, Buffett & Archer (2004) Coal, oil, gas: reserves economically exploitable at current market prices Gas Hydrates: total marine inventory

Hydrate Exploitation

Methane gas may be produced from hydrate deposits via:

• Pressure reduction

• Temperature increase

• Addition of chemicals (incl. CO2)

Hydrate Exploitation

Energy balance for gas production via heat addition at Blake Ridge (Makogon et al. 2007) 2000 m water depth, two ~3 m thick hydrate layers ~40 % of the potential energy can be used for energy production while ~60 % of the potential energy is lost during development, gas production, and transport Japanese Hydrate Exploitation Program Hydrate exploitation via pressure reduction has a much better energy balance and may be economically feasible at an oil price of ~54 $/barrel.

CH4(g)-Recovery from Hydrates Exposed to CO2

after 200 h in sandstone CO2(l) Kvamme et al. (2007)

CO2(l) Hiromata et al. (1996) after 400 h

CO2(g)/N2(g) Park et al. (2006)

CO2(g) Lee et al. (2003) after 5 h

after 15 h

Spontaneous exothermic reaction !

Field production tests (USA, Japan, South Korea)

On-shore Alaska (Prudhoe Bay, below permafrost) 2012 (DOE, ConocoPhillips, Japan): CO2 injection (short-term) 2012 – 2014 (DOE, BP, Korea): Pressure reduction (long-term) Off-shore Japan (~1000 m water depth) 2012 (MH 21): Pressure reduction (short-term) 2014 (MH 21): Pressure reduction (long-term) Off-shore South Korea (~2000 m water depth) 2014: Pressure reduction and CO2 (short-term)

The SUGAR Project

• Funded by German Federal Ministries (BMWi, BMBF)

• First funding period: July 2008 – June 2011

• Total funding: ~13 Mio € (incl. support by industries)

A: Exploration

A1: Hydro-acoustics

A2: Geophysics

A3: Autoclave-Drilling

A4: Basin Modeling

B: Exploitation and Transport

B1: Reservoir Modeling

B2: Laboratory Experiments

B3: Gas Transport

Prospection

Exploration

Quantification

Exploitation/ CO2 Storage

Pellet Transport

The SUGAR Project

Project Academia Industries A1 IFM-GEOMAR L3 Communications ELAC Nautik

GmbH

A2 IFM-GEOMAR, BGR Hannover K.U.M. Umwelt- und Meerestechnik GmbH, Magson GmbH, SEND Offshore GmbH

A3 University of Bremen, TU Clausthal

Bauer PRAKLA Bohrtechnik GmbH

A4 IFM-GEOMAR Schlumberger-IES

B1 Fraunhofer UMSICHT, GFZ Potsdam, IFM-GEOMAR

Wintershall, Aker-Wirth GmbH

B2 FH Kiel, GFZ Potsdam, Fraunhofer UMSICHT, IFM-GEOMAR, Uni Göttingen

BASF, CONTROS GmbH, R&D Center at FH Kiel, 24sieben Stadtwerke Kiel AG, RWE Dea, Wintershall, E.ON Ruhrgas AG

B3 IOW, FH Kiel Linde AG, Meyer Yards, Germanischer Lloyd, BASF

SUGAR Partners

SUGAR Technologies

- Hydrate deposits are often formed by gas bubble ascent while some gas escapes into the water column

- Multi-beam echo-sounder systems have been developed and equipped with software-based automatic bubble detection AOD) system

- Field tests: Dec. 2010 (Black Sea) and March 2011 (off New Zealand)

A1: Hydro-acoustic detection of hydrate deposits

Detection of gas bubbles and flares by AOD, Danube area, Black Sea

A2: Geophysical imaging of hydrate deposits - Improved deep-towed seismic and electromagnetic systems, 3-D seismic

system (P-cable) and stationary CSEM system for 3-D application have been built.

- Field tests: Dec. 2009 (Med.), Dec. 2010 (Black Sea) and March 2011 (off New Zealand)

Set-up of deep-towed streamer and raw data acquired off New Zealand with improved resolution of blanking zones by undershooting

A2: Electro-magnetic imaging of hydrate deposits

CSEM set-up and data acquired off New Zealand

A2: Joint inversion of seismic and CSEM data

Location of gas-bearing layer and quantification of gas content by joint inversion at a mud volcano off Egypt

A3: Autoclave-drilling technology

- Autoclave-systems for MeBo and formation-independent deep-sea drilling (SUGO) have been built.

- Field tests: Aug. 2010 (SUGO, off Korea), March 2011 (MeBo, Black Sea)

Set-up of SUGO Deployment of MeBo

A4: Basin Modeling - New version of PetroMod3D simulating the temporal evolution of the

Hydrate Stability Zone during basin formation has been developed and is now available for the customers.

- Simulation of hydrate accumulation at the Alaska North Slope is underway (in cooperation with US-GS)

A4: Basin Modeling

Initial results for Alaska North Slope with new PetroMod release

B1: Reservoir modeling

- Extended versions of the STARS reservoir model and an in-house code have been developed and successfully applied to simulate natural gas production from hydrates via CO2 addition.

- Generic hydrate reservoir model applied for the simulations.

- Similar hydrate reservoirs occur off China, India, Japan and in the Gulf of Mexico

B1: CO2- and CH4 hydrate stability in seawater

Source: Duan & Sun (2006)

The reservoir pressure is reduced to 50 - 60 bar at the production well. Under these conditions (P = 50 – 60 bar, T = 8 – 8.6°C), methane hydrate is decomposed into gas and water while the injected CO2 forms CO2 hydrate.

(Huff‘n‘Puff) (Huff‘n‘Puff)

(2-Hole-Approach) (2-Hole-Approach)

Saturation CH4 hydrate after production

Saturation CO2 hydrate after production

t = 2880 days t = 2880 days

t = 1826 days t = 1826 days

Phase 1: CO2 injection (1yr.) Phase 2: Closed well (0,5yrs.) Phase 3: production (6,5yrs.)

B1: Gas production via CO2 injection and pressure reduction

240 m

20 m

B1: Gas production via CO2 injection and pressure reduction

Time (d)

Gas

pro

duct

ion

rate

(x10

³ Nm

³/d)

Gas

pro

duct

ion

(cum

. x10

³ Nm

³)

2-Hole

Huff‘n Puff

Composition of produced gas: ~99% CH4, ~1% CO2

B1: Methane gas recovery after 5 years

Pressure reduction

Pressure reduction and CO2 injection (2 Hole, liquid CO2)

Pressure reduction and CO2 injection (Huff‘n Puff)

20 %

15 %

27 %

B2: Laboratory experiments

- High-pressure labs were set-up at GFZ-Potsdam, IFM-GEOMAR, Univ. Göttingen, and Fraunhofer UMSICHT.

- In-situ composition of methane has been tested successfully at GFZ-Potsdam with 10% Pd-ZrO as most robust and efficient catalyst.

- Polymers accelerate methane hydrate decomposition and CH4-CO2 gas exchange in hydrates significantly (BASF, Univ. Göttingen)

- Methane hydrates are exposed to supercritical CO2 to accelerate methane gas production from hydrates (IFM-GEOMAR). First results indicate rapid and efficient methane release from hydrates exposed to super-critical CO2.

- Mechanisms of gas exchange in hydrates have been studied using Raman microscopy and XRD (IFM-GEOMAR, GFZ Potsdam, Univ. Göttingen)

B2: Mechanisms of gas exchange

With liquid and gaseous CO2, the exchange reaction proceeds in 2 steps: a faster surface reaction at beginning followed by a slower permeation-controlled gas exchange, max. 50 % gas recovery due to formation of mixed CO2-CH4 hydrates (W. Kuhs, Univ. Göttingen)

CH4-recovery from hydrates in sand matrix exposed to CO2

Phase diagram for Black sea conditions

Bottom water temperature too high for CO2 production method. Method of choice: Pressure reduction

B3: Gas transport - Optimized production process for methane hydrate pellets has been

developed (Linde). Only ~3 % of the methane energy content is lost during this process.

- Self-preservation mechanisms have been studied. Pellets are stabilized by a thin ice skin.

- Carrier vessel concepts have been assessed (Meyer Yards).

gas

Gas Hydrate

Ice

July 2011 – June 2014 (funded by BMWi, BMBF and RWE Dea)

A: Exploration

A1: Hydroacoustics & Sensors ELAC Nautik, CONTROS, IFM-GEOMAR A2: Geophysics & Drilling TEEC, CORSYDE, CONTROS, IFM-GEOMAR, BGR, MARUM A3: Basin Modeling Schlumberger AaTC, IFM-GEOMAR B: Exploitation B1: Reservoir Modeling Wintershall, EON Ruhrgas, Fraunhofer UMSICHT, GFZ, IFM-GEOMAR B2: Laboratory Experiments RWE Dea, BASF, CONTROS, Fraunhofer UMSICHT, GFZ, Univ. Göttingen, IFM-GEOMAR B3: Drilling technologies Bauer, Aker-Wirth, TU Clausthal, TUB Freiberg, Univ. Bochum

SUGAR Phase II

Major aims: - develop gas hydrates as an environmentally sound natural gas resource and medium for CO2 sequestration

- quantify gas hydrate masses and distributions in the sub- surface via enhanced geophysical exploration, data analysis, and basin modeling

- enhance methane hydrate dissociation, methane gas release and CO2 sequestration via a suitable combination of super- critical CO2 and polymer injection, in-situ combustion, and depressurization

- reduce development and production costs and environmental risks by improved drilling and production technologies

SUGAR Phase II

Bulgaria, Georgia, Romania, Russia, Turkey, Ukraine (Black Sea): Joint exploration cruises, joint workshop (March 27th – 28th, 2012) New Zealand: Joint exploration cruises (2011) US: Numerical basin simulation Alaska North Slope (2011 - 2014) France (Total): Joint exploration cruise off West Africa (2012) Taiwan: Joint exploration cruises (2013) India: Joint workshops, CLIENT proposal, pending Brazil (Petrobras): CONEGAS project, joint exploration cruise (pending) Japan, China, South Korea: Joint workshops and meetings UNEP: Report on gas hydrates (2012) EU: Coordinated program on environmental risks of sub-seabed CO2 storage (ECO2: 2011 - 2015) International off-shore field production test with CO2 injection (~2015)

International contacts and cooperations