IPTC 17708

Fuelling the Future with Gas Hydrates as a Perpetual Energy Source

K. Steffones, Krishna R. Chaturvedi, Priya Sihag, University of Petroleum and Energy Studies, Dehradun



Copyright 2014, International Petroleum Technology Conference

This paper was prepared for the International Young Professionals Competition at the International Petroleum Technology Conference held in Doha, Qatar, 2022 January 2014.

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Introduction

Gas hydrates are crystalline compounds that form when water (or ice) contacts small molecules (called
hydrate guests) under certain pressure and temperature conditions. The correct chemical name should be
gas clathrate hydrates, with a clathrate being a compound formed by the inclusion of molecules of one
kind in the crystal lattice of another (water in this case). In practice, these compounds are commonly
referred to as gas hydrates, clathrate hydrates, or just hydrates. While specific to the particular hydrate
guest, gas hydrates are stable typically at high pressures and low temperatures. A wide range of
molecules have been shown to form gas hydrates. Those of the most practical interest are light
hydrocarbons such as methane, ethane, and propane. Carbon dioxide and hydrogen sulfide also form
hydrates and are of particular interest. When hydrates form, water crystallizes to create a lattice of
molecular-sized cages that trap guest molecules without chemical bonding between the host water and
the guest molecules. (Fig 1)

The potential use of gas hydrates as an energy resource should be viewed from two perspectives. The
first concerns global energy needs from a relatively long term point of view (about 50 years). The
second is related instead to geopolitical concerns and national energy security. The current rate of
natural gas consumption versus production should ensure availability for more than 60 years.
Gas hydrates are present in large amounts in all of Worlds oceans on the continental shelves and in
permafrost areas. Whether onshore (including Canada, Russia, China, USA) or offshore (USA, Japan,
India, and others), hydrates are present in countries which are large consumers and importers of energy.
Fig 1.

The inclusion or trapping of gas molecules in
the gas hydrate lattice. The molecular-sized
cages are composed of hydrogen bonded
water molecules.(Reproduced from
SETARAM)
2 IPTC 17708
As an energy resource, gas hydrates are considered as unconventional hydrocarbon resources which are
either expensive to recover and/ or requiring special technology for extraction. However, in recent years,
production has begun on this unconventional resource. It was necessary to better understand the geology
and properties of the reservoirs to address the production challenges. While hydrates for some are a
potential future energy resource in the coming decades, countries like Japan have already identified
hydrates as a strategic resource and have well-defined projects ongoing to commercially produce
hydrate. Besides the best known countries working on hydrates (Canada, China, India, Japan, South
Korea, USA, etc.), other countries (e.g., Bulgaria, Taiwan, and Turkey) are undertaking research to
evaluate and define their national reserves of gas hydrates.

CONCEPTUAL MODEL-

A model may be defined simply as a purposeful representation or a description of a system of interest. A
conceptual model for the methane from the methane gas hydrates by sequestered Carbon dioxide and
then the conversion of carbon dioxide into methane by microbial action, namely methanogenesis is
being proposed in this paper.

Perpetual Cycle-
In this process the Methane hydrate reservoir is injected with Liquid Carbon Dioxide CO
2
and Nitrogen
(N
2
) Gas mixture for the production of Methane (CH
4
) gas from

the hydrate reservoir. After the CO
2

exchange production method about 50% of Carbon dioxide gas CO
2
remains in the hydrate reservoir in
the form of CO2 hydrates and void age gas. Now this CO
2
Hydrate can be dissociated to release Carbon
dioxide gas into the reservoir. Released Carbon dioxide gas is converted into Methane gas by the action
of injected microbes (methanogenesis). Once the Methane gas is formed the temperature and pressure
condition of the reservoir is changed to provide exact conditions for the formation of Methane hydrate
and thus methane hydrate forms. Once the Methane hydrate is formed we can again start the process of
the hence continue the cycle, extracting large amount of Methane from a single reservoir.

Process in Detail

Consider a reservoir with reservoir pressure with 9000kpa and reservoir temperature 278.15K (5
o
C) and
in the payzone of reservoir contains 100 percent methane hydrates only. Few gases such as ethane,
propane are present in trace amounts whose effect neglected. For this reservoir conceptual model is
applied. Gas exchange CO
2
/CH
4
method is done for production. This process has been same as done for
the Ignik Sikumi #1 well in North Slope Alaska region.

For the injection phase, all injection was performed below parting pressure of the formation.. Then CO
2

N
2
mixture is injected into the wellbore along with chemical tracers for predetermined injection period.
After the aforesaid, there is the Initiation of Microbial Injection in wells where CO
2
production is not
taking place anymore. Here, the microbes are injected downward with warm water and nutrient media
akin to the microbial enhanced oil recovery process. The microbes are given time to act and carry out
conversion of carbon dioxide to methane. The temperature and pressure ranges are so altered so as to
inhibit the formation of carbon dioxide hydrates and initiate the formation of methane gas hydrates.

The efficiency of both, CH
4
production and CO
2
retention is best at 8 C, 13 MPa. Here, both CO
2
- and
CH
4
-hydrate as well as mixed hydrates can form. At 2 C, the production process will be less effective
due to congestion of transport pathways through the sediment by rapidly forming CO
2
-hydrate.Mass and
volume balancing of the collected gas and fluid stream identified gas mobilization as equally important
process parameter in addition to the rates of methane hydrate dissociation and hydrate conversion. Thus,
IPTC 17708 3
the combination of heat supply and CO
2
injection in one supercritical phase helps to overcome the mass
transfer limitations usually observed in experiments with cold liquid or gaseous CO
2
.



Methane gas is recovered using depressurization method, leaving behind Carbon dioxide hydrates in the
reservoir. During the complete process reservoir temperature was reduced by a few kelvins due to
reduction in pressure of the reservoir. After that hot water is injected into the reservoir to increase the
reservoir temperature to 284.65K (11.5
o
C). Thermal Stimulation method is applied to reservoir in order
to increase the temperature until a temperature suitable for methane hydrate formation (as it requires a
higher pressure and temperature range than the carbon dioxide hydrate formation conditions).

This thermal stimulation causes CO
2
hydrate to break and release free carbon dioxide gas in to reservoir.
After hot water injection methanogenic bacteria are injected in the reservoir. The process will be similar
to the underground microbial enhanced oil recovery Microbial flooding recovery.

Methanogens present in the reservoir will convert the Carbon dioxide gas present into Methane gas.
Once methane gas is produced inside the reservoir Methane hydrate will be formed in the reservoir as
temperature and pressure conditions are above the methane hydrate stability region.

METHANOGENS & METHANOGENESIS-
Methanogenesis is the formation of methane by microbes known as methanogens. Organisms capable of
producing methane have been identified only from the domain Archaea, a group phylogenetically
distinct from both eukaryotes and bacteria, although many live in close association with anaerobic
bacteria.
BIOCHEMISTRY OF METHANOGENESIS-
Methanogenesis in microbes is a form of anaerobic respiration. Methanogens do not use oxygen to
respire; in fact, oxygen inhibits the growth of methanogens. The terminal electron acceptor in
Fig 2.

Carbon dioxide injection to produce from a
methane gas hydrates well (sourced from
CHEVRON).
4 IPTC 17708
methanogenesis is not oxygen, but carbon. The carbon can occur in a small number of organic
compounds, all with low molecular weights. The two best described pathways involve the use of carbon
dioxide and acetic acid as terminal electron acceptors:
CO
2
+ 4 H
2
CH
4
+ 2H
2
O
CH
3
COOH CH
4
+ CO
2
The reduction of carbon dioxide into methane in the presence of hydrogen can be expressed as follows:
CO
2
+ 4 H
2
CH
4
+ 2 H
2
O
Some of the CO
2
is reacted with the hydrogen to produce methane, which creates an electrochemical
gradient across cell membrane, used to generate ATP through chemiosmosis. In contrast, plants and
algae use water as their reducing agent.
A few microbial sources that can be used are Methanogenium frigidium, Methanococcoides burtonii,
Methanolobus pschrophilus R15, Methanosacrina lacustris.

Out of all the above, M.burtonii may be considered as the best candidate for the conversion process as it
can survive at temperatures below 0
o
C. The nutrient medium injected along with the microbes must be
such that it does not react with the hydrates structures in the formation. A similar approach like the
Enhanced Oil Recovery by Microbial flooding can be used and be put into operation with minimal
changes.





ADVANTAGES OF PROPOSED CONCEPTUAL MODEL-
Higher recovery than any other conventional method of recovery of methane from gas hydrates
reservoirs.
Since the process involves the recovery of methane multiple times, the conventional recovery volumes
are boosted hence improving recovery efficiency. With each step of microbial action, more CO
2

hydrates would be converted into CH
4
hydrates and be ready for recovery in the next injection phase.
This process is seemingly perpetual and may be a very efficient method for recovery from hydrates.
Carbon Capture and Sequestration
Research work has shown that the amount of carbon dioxide (CO
2
) released into the atmosphere has
increased significantly since the beginning of the industrial era (i.e. starting the 19
th
Century). Unless
something is done to reduce the amount of CO
2
entering the atmosphere, the world will continue to
experience the effects of climate change. Carbon capture and storage (CCS), sometimes called carbon
capture and sequestration, prevents large amounts of CO
2
from being released into the atmosphere and
causing the Greenhouse effect. The technology involves capturing CO
2
produced by large industrial
plants, compressing it for transportation and then injecting it deep into a rock formation at a carefully
selected and safe site, where it is permanently stored. Here we will use the capture CO
2
for injection into
the hydrate reservoirs, tackling two problems at once, i.e., reducing the amount of CO
2
in the
atmosphere and generating energy via its injection and conversion to methane.
THE WAY AHEAD-
In the coming future, the demand for energy is only going to rise and given our current lack of
alternative resources, it is bound to affect our ability to sustain our development rate. Natural gas is
widely expected to be the fastest growing primary energy source in the world over the next 20 years. In
the U.S. Energy Information Administration's International Energy Outlook 2002 (IEO2002) reference
case, worldwide gas consumption is projected to almost double to 162 trillion cubic feet in 2020 from 84
trillion cubic feet (standard conditions) in 1999. Given the attractive features of gas hydrates, and the
IPTC 17708 5
growing demand for natural gas, it seems reasonable to conclude that gas hydrates could serve as a
future energy resource. Newer methods and technologies must be developed in order to more effectively
harness our existing resources like the abundantly available methane gas hydrates. Two factors make gas
hydrates attractive as a potential energy resource:
(1) The huge volumes of methane that is apparently trapped as clathrate within the upper 2000 m of the
Earth's surface.
(2) The wide geographical distribution of gas hydrates.

The innovative conceptual model that we propose provides altogether a new outlook on gas hydrates.
The model combines the advantages of the two processes Methane production from injection of Carbon
dioxide into reservoir and Methanogenesis which will create a form of perpetual energy source and
would substantially increase the production of natural gas from hydrate reservoirs and will act as form of
Carbon-capture and sequestration (CCS).Use of microbes of to convert the sequestered Carbon dioxide
in hydrate form to Methane hydrate holds a huge potential to act as a promising fuel of future. And if
this perpetual cyclic model is acknowledged for Methane gas hydrate reservoir, then from a single
reservoir unimaginable amount of Methane can be produced. Though this process is akin to a perpetual
energy source, any such process is technically unviable.
However, this method has the potential to drastically improve methane production. The demand for
energy is only expected to rise in the future, driving the conventional energy scouts towards the
unconventional and more exotic venues liked Methane Gas Hydrates. Newer and more innovative and
out of the box thinking must be encouraged to solve the dilemma of satisfying our futures growing
energy needs. Truly, its unlocking energy through innovation, technology and capability to fuel our
futures growth and the key towards attaining sustainable growth.


Fig 3.

The percentage of energy
sources used over the years
(sourced from EIA).