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The Present and Future Role of Gas and


Gas Hydrate in Energy Supply
Zhihong XU and Hao WEN
Laboratory of Multi-phase Reaction, Institute of Process Engineering, Chinese
Academy of Sciences, No.1, 2nd North Lane, Zhongguancun, Beijing 100080, China

Abstract
The amount of natural gas resources has a tendency of quickly increasing both on the
exploration and exploitation in recent years. In addition to natural gas (NG) energy, huge
amount of natural gas hydrate( NGH)deposited resource has also been discovered in Arctic
Pole and under the ocean in the last phase of 20th century. It is estimated the NGH quantity
about two or three times of all fossil fuels being discovered. So, in the following, a series of
most important problems about gas energy will be discussed. In the meanwhile, a series of
using properties of gas hydrate created new processing methods have also been introduced.

1 The Coming Gas Energy Age


From 1850 to 2100, the main fossil energy resource has been changed several
times, i.e. from wood to coal, from coal to petroleum, and now owing to many reasons,
especially the huge resource of natural gas hydrate (NGH) discovered, it looks like we
will be gradually from petroleum age shifted to gas energy age. WEC published the
past 150-year global primary energy substitution, as indicated in Figure 1 [1].

Figure 1 Global primary energy substitution, historical development from 1850 to 1990 [1]

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Of course, the so-called gas energy age (or post-petroleum age) does not mean
petroleum will be stopped to use, but owing to the quick raising price of petroleum, it
will force people to find other more inexpensive, clean and efficient substitutes. So,
more exact to say, the ratio of gas energy will be increased in coming years and the
petroleum will soon pass the dominant position.
From the global point of view, coal, petroleum, nuclear energy and other fossil
fuels will also be in use simultaneously in the gas energy age, but gradually not in
dominant position. In between the mid of 21st century, the importance of gas energy,
especially the gas hydrate, will be gradually increased from a subsidiary to a dominant
role.
However, this is not absolute exact for some local area. In some local area, even
coal is in the dominant position yet; and in some other local area, petroleum is still
abundant enough to support the local economy for a long time period.
From Figure 1, we may expect at the end of 21st century or at early in 22nd century,
nuclear energy and sustainable energies may take over the dominant position, when it
increased to a certain extent.
From historical point of view for human beings, the dominant ages of energies
may be changed step by step. A summary of above-mentioned may be listed in the
following manner: wood energy  coal energy  petroleum energy  gas and
sustainable energy  nuclear and sustainable energy.

2 Gas Energy and Its New Discovery


In recent years, people pay more attention to the clean gas energy. In addition to
the traditional natural gas, natural gas hydrate (NGH), coal bed gas (CBG) and many
processing gases have been discovered. Experts intensify their efforts on the studies of
NGH’s properties [2-4], exploration, exploitation and a series of new ways of its
application [5-8]. The NGH’s property study results guide us to find new methods for
gas hydrate exploiting, and provides chance to develop new processing methods of
using NGH formation and dissociation behaviors.
In addition to natural gas, NGH and CBG, there also exist many other processing
gases in the world, e.g. bio-fermented gas, coke oven gas, petroleum refining gas, coal
processing gas, metallurgical processing gas, shale oil processing gas, tar sand
processing gas etc. Owing to many reasons, some processing gases are often not used
rationally, especially in the developing countries. With the aid of forming gas hydrate,
it may help us to find new ways to use gas energy effectively. It will be mentioned in
last part of this paper.

3 LNG, CNG and LPG


In gas energy age, we may often meet the terms of LNG (liquefied natural gas),
CNG (compressed natural gas), LPG (liquefied petroleum gas), CBG (coal bed gas)
and NGH (natural gas hydrate).
LNG is a commercial method for over ocean transportation of natural gas. LNG
will be vaporized at the receiving station and disseminated to the terminal users via
local gas pipeline system or in the form of CNG. In the last decade, the LNG
production has a very big increase, now its user is extended to the whole world. A
series of experiments for directly using LNG instead of petroleum products have been
published [9].

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However, some problems [10] or even controversial ideas still exist in using LNG:
(1) low temperature of 161 C is required to transform natural gas into liquid state,
which is an energy-consuming process; and (2) a series of LNG storage tanks at the
receiving station may bring disaster possibilities causing by thundering, mis-operation,
terrorism attack or military attack etc., and it will be difficult to find the rescue
methods when disaster happened [11,12]; (3) it needs a deep chilling system for long
time storage, so it looks like uneasy to use as the mobile engine fuel.
Hence, (1) for the energy consumption, it is necessary to integrate some processes
for recovering the cold energy; (2) for the extra big metropolitan cities, it is better to
select other ways of natural gas storage instead of LNG; (3) for the mobile engine fuel
it can only be used for heavy truck or train for time being.
CNG may be taken as engine fuel with lower price than gasoline, from the
present market price. Some kinds of materials can be used as the CNG container,
where steel or composite materials may be the basic inexpensive materials. However,
a big CNG supporting network system is required to facilitate the users to get CNG
everywhere, when using CNG instead of gasoline as the engine fuel.
LPG may be obtained from two ways, one is from the light hydrocarbons
contained in petroleum or natural gas, and another is from the coal and petroleum
processing gas. It can be directly used as the substitute of gasoline or as raw materials
of chemical industry. It can be stored in liquid form under moderate pressure.
In summary, it should be emphasized that the gas energy is a cleaner energy than
coal and petroleum, but more expensive than coal in most countries. The technical
progresses on improving the efficiency of using gas energy should be advocated for
compensating the price difference.

4 Coal Bed Gas (CBG or CBM)


In the traditional coal mining process, people have to dilute and expel CBG into
atmosphere by using large-scale fan. Sometimes the disaster of coal mining may be
happened due to the CBG explosion.
At the end of last century, people found the CBG deposited with coal bed together,
which can be recovered as a gas energy resource in most cases [13]. Most of the
explosion disaster in coal mining process can be avoided, if people can extract CBG
out before coal exploitation. Thus, we may say this is a double-win business, i.e.
getting new gas energy on one side, and helping to solve the mining disaster problem
on the other side.
CBG should be treated as a new energy resource, and to acquaint the peculiarity
of CBG exploitation. There may be three kinds of CBG: (1) CBG exploited before
coal mining; (2) CBG expelled during digging the channel for coal mining; and (3)
CBG expelled during the coal mining. For the first kind CBG the depth of CBG well
only needs several hundreds meters but not several thousands meters like natural gas
well needed, and it can be used economically with no serious problem. For the next
two kinds of CGB, research works on gas recovery are needed. We need to give some
favorable policy to solve the problems existed.
The price of CBG will be determined on many factors. The price of first kind of
CBG may be lowered to compete with gasoline, if the exploration and exploitation
staff is well trained with high quality.
Summarized the above mention we may say CBG is a new energy but with
challenging. It deals with crossing disciplinary of geology, coal mining technology,
environmental protection, security to prevent disaster and application engineering.

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The governments should set up a series of policy to help this double-win business
being realized in order to get a new energy, to reduce the pollution and to avoid the
coal mining disaster. The United Nations should encourage the developed countries to
help the developing countries to recovery CBG as much as possible [14-15]. We
expect this kind of cooperation will be more and more.

5 Natural Gas Hydrate (NGH)


Villiard synthesized the hydrates of light hydrocarbon gas (CH4 , C2H6, C2H4 etc.)
in his laboratory in 1888. In 1934, Hammerschmidt discovered the natural gas
pipeline often being plugged by NGH. Hence, a series of inhibitors has been studied
and used to avoid natural gas pipeline plugging formation.
After several decades, the huge deposited gas hydrate resources under the Arctic
Pole and the ocean bed have been discovered. Many exploration and research works
are carried out in many countries, and the huge amount of gas hydrate deposited
attracted people to drop investment. Now in accordance to people’s estimation, the
first commercial gas production from NGH might be realized around 2015. However,
we have not found the detailed economic evaluation data published so far.
In fact, before the commercial successful exploitation of NGH, the basic studies
on the properties of NGH has been carried out for quite a long time and accumulated
many basic property data. It may help us to solve the problems of gas exploitation,
storage, transportation, dissemination and purification in practice.
Exploration and exploitation of NGH
From technical point of view, the exploitation of NGH may have different ways:
(1) NGH can be dissociated using inhibitors, e.g. methanol or other inexpensive
chemicals, the natural gas and inhibitors can be recovered after lifted to the platform
through a gas lift pipeline; (2) the natural gas in NGH may be substituted by heat and
CO2 under several hundreds meters of ocean from deposited NGH layer; (3) NGH can
be melted and dissociated by low pressure steam, and the condensed water can be
pumped out for recycling use.
From environmental point of view, it seems to be reasonable if we use low
temperature dry solid CO2 to implement two functions, one is using CO2 to expel
methane, and another is using the solidified CO 2 (78 C of CO2) to chill the lifted
natural gas into NGH again on the platform for shipping to the terminal users.
In summary, two kinds of conditions are required in order to exploit NGH under
300 1000 meters ocean, i.e. inhibitor, or heat.
Transportation of natural gas in form of NGH
At present, two commercial methods exist for natural gas long distance
transportation, by pipeline or by LNG ocean shipping. For the former method, it needs
to drop a heavy investment and sometimes needs passing through several countries.
For the later, it needs to spend a lot of energy to get and keep low temperature of
161 C, and also to build a series of LNG receiving station, which needs fire
protection facilities.
In the last decade, people intensify their efforts on developing the new method of
long distance transportation for natural gas in form of NGH [16-19]. With the help of
NGH property study, Mitsui [16-18] and its cooperators are building a ship for natural
gas transportation in the form of NGH instead of LNG. The first ship will be finished
in near future. We believe this new method will soon be emerged and may gradually

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take the place of LNG, because energy consumption of NGH may be lowered nearly
30 40% than that of LNG and the security problem may easily be solved.
There will be at least two routes for NGH manufacturing, a continuous process to
produce gas hydrate ball [16-18] and a batch process using pressurized tank. For the
later it can be realized from point-to-point connection, i.e. from NGH production
place to the terminal users directly [20].
NGH may also be used in the purification and enrichment of CBG and other
processing gases. In CBG, methane is easier to form hydrate than N 2 and O2. The
methane content of CBG may be enriched from 60 70% to 85 95%, in the hydrate
phase.
People need the help of thermodynamic, and also the kinetic data to guide the
process of dissociation or formation of NGH. For the case of NGH formation, people
need to provide the 3-phase of natural gas–water–hydrate co-existence conditions. In
other words, the hydrate crystal should be growing with existence of natural gas at
chilling condition. Otherwise, the water will be changed to ice or only a small amount
of natural gas can enter the crystal cage.
It is well known that NGH will be an inexpensive and safe alternative for gas
storage and transportation in near future. In case it becomes a commercial method, it
might also be an adequate method for the local area or national strategic storage of
natural gas.

6 Energy Supply for Chemical Industry


At the first half of 20 th century, coal instead of wood acted as main raw material
for chemical industry. The volatiles in coal had been extracted and used extensively.
The coal is also used for iron making, power production and gasification for further
chemical synthesis.
Petroleum toke the place of coal to be the raw materials for chemical industry
after 2 nd World War. The main reason of the rapid development of petrochemical
industry is the low price of petroleum (around 5 7 USD/barrel). Many large-scale
petrochemical processes have been developed, which push the price of chemicals fall
down and initiate the mass scale petrochemical production in the last fifty years in
20th century.
The fast raising price of petroleum force some chemical industry shifting their
raw materials from petroleum to natural gas and other processing gases. Generally
speaking, several ways from gas materials to chemicals (so-called GTL, i.e. from Gas
to Liquid) exist: (1) direct conversion of natural gas to ethylene [21,22], and
producing many further chemicals; (2) direct synthesis of methanol, gasoline or diesel
fuel etc. [23-29] via syngas [30-35]; (3) from methanol to produce ethylene, di-methyl
ether (DME) [36-38] and gasoline etc.; (4) production of ethylene or other
hydrocarbons from recovered C2 C4 fractions in petroleum refining or gas; (5)
production of hydrogen or other petrochemicals from the byproducts or processing
gases, e.g. coke oven gas [27].
The biggest GTL manufacturer for synthesis of gasoline and gas oil is being built
on the natural gas site in the Middle East, from which the manufacturer can obtain the
inexpensive raw materials and low construction investment [36].
The other low-cost method for obtaining the raw materials is from the processing
gas. In case of using coke oven gas, it may extract out the 25% methane as solid NGH,
and then to get the rest gas with nearly 80% H2 and 15% CO. It can be processed to
obtain the inexpensive hydrogen product.

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Another big amount of energy may be come from the recoverable plastic
materials, e.g. wrapping materials, farmer used film, city used plastic bag etc. The
recovered plastic will be the best feed for chemical industry, if it can be separately
recovered. For the iron and steel making industry, in some developed countries, the
recycling feed may arrive or even more than 50%. For the plastic production we also
advocate the recycling feed to enlarge the raw energy resources.

7 Disaster, and Risk Prevention in Gas Energy Age


People have to face worries about the safety problems in the coming gas energy
age.
People knew NGH from the plugging of natural gas pipelines. A series of
measures, e.g. many inhibitors have been studied and used to prevent the plugging
accident. Now people can avoid this kind of disaster.
Now, the LNG shipping and receiving stations are expanded fast in the world.
Some people in California (USA) worry the security problem of building the LNG
receiving station closed to the metropolitan cities. This is the right people ought to
have. Any plan of setting the LNG receiving station, should be approved by the local
congress, and tell them what benefit they will have, what things they need to obey,
and what security problem exists. People dealing with the LNG production, shipping
and storage should be exactly under control, and managers must very clear that it
looks like no effective way to stop the fire disaster once it is started. This kind of
discussion of contradictory ideas is always necessary and helpful, even people cannot
approach the result at present.
From the security and energy-saving points of view, scientists studied the
geological mechanism of NGH formation, and imitate the mechanism in laboratory.
Now it looks like to be possible to reproduce NGH artificially in commercial scale.
This success presents the possibility of developing commercial NGH storage
economically and safely in near future. NGH may become an attractive way for
natural gas storage once it is success in practice, because NGH is relatively inert to
fire dangers, and it might be possible in use for fuel even in natural disaster. Scientists
expect people can have the possibility to select NGH instead of LNG, especially for
the metropolitan cities.
People are gradually aware that the gas suddenly being released from under-ocean
NGH might be the reason of causing ship disasters in the Bermuda Triangle in
Atlantic Ocean. The natural phenomena tell us that the exploitation of the ocean bed
deposited NGH has to be going on very carefully without interfering the silent
surrounding of ocean bed.
A series of new security problems will be accompanied with the exploitation of
NGH when people need to take out the bounded gas. From macro-scale point of view,
the exploitation should be in a closed space with middle pressure surrounding, a pipe
brings energy or materials into the system and a pipe brings natural gas and water out
of the system. All of the mining works have to be performed in a closed system,
without permitting even a minute part of gas or agent out, when heat or agent is
introduced to NGH to drive out the gas. Any opening operation does not be permitted.
From above discussions, it is clear that the exploration and exploitation of NGH
should be carried out carefully, extensively and jointly.
Many companies may be involved into the business of NGH exploitation. Some
common rules, especially the security rules on the NGH exploration and exploitation
should be set up by the United Nations, and it ought to be obeyed for all countries.
Otherwise there will be many contradictory issues happened.

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8 Energy Saving Strategy for Gas Energy Age
People should understand the gas energy couldn’t only be used as a simple
substitute of coal. Due to high expense of exploration, exploitation and the long
distance transportation, it ought to have higher efficiency of energy electricity
conversion, and also needs to use the exhausted heat as the heat-electricity
co-production.
The coal efficiency of heat-electricity conversion may approach to 30 40% in
some advanced power stations. For the power stations using gas fuel, the efficiency of
heat-electricity conversion ought to arrive to 48 52%. Furthermore, people now
concentrate efforts to approach higher efficiency to 60% by fuel cell joined with gas
turbine [40].
Many cities want to use natural gas instead of coal as directly burning fuel in
order to improve the atmosphere quality. In this case, sometimes people have to pay
fuel fee for natural gas as two times as for coal.
It is possible to lower down the price of final electricity product for the power
station using gas energy by following ways: (1) to build big power stations in-site of
gas field, the fuel price will be lowered 2 3 times than long distance transportation
via pipeline or LNG shipping; (2) to provide the gas fuel in the form of NGH with
point-to-point supply; (3) using some processing gas as combine cycle fuel, e.g. low
grade CBG; coke oven gas; metallurgical processing gas.
It is also possible to recover certain amount of cold energy from LNG with the
well-designed energy recovery system.
The United Nations should advocate people to set up rules to promote the use of
gas energy with high efficiency. And the local government ought to use the tax
measures to guide the gas energy using effectively. If people simply use the gas as
directly burning fuel to provide heat only, it would be added tax to some extent to
advocate the electricity-heat co-production.

9 The Relationship of Gas and Sustainable Energies


Sustainable energies are clean, renewable energies. It is worthy for us to develop
the hydropower, wind power, solar power, bio-fermented gas, earth heat etc. as fast as
possible. However, the scale of sustainable energies is not big enough right now,
which can only play a complementary role to the traditional fossil fuel energy at
present.
Another reason is that the sustainable energies are time-dependent, which usually
could not fully meet the requirements of power supply network system. The power
stations using gas fuel can easily be started and shut down, which can be used as a
measure to balance the peak of power supply network. It means in the gas energy age,
the more efficient way is the gas energy being developed together with the sustainable
energy, and complementary to each other.
The sustainable energies ought to be developed as fast as possible, even in the gas
energy age. From long-term point of view, the gas energy is more expensive after the
long distance transportation, while the sustainable energies are easily to produce and
use in local area.
For the international society, we have to notice that the main function of gas
energy is to be a supplement of petroleum shortage, gradually to undertake the main
duty both in energy supply and in chemical industry at the beginning of gas energy
age. The gas and sustainable energies will be complementarily used for the cooking,

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air conditioning and heating system. The sustainable energies should undertake the
main role gradually with the progress of science and technology.
Some well-developed countries will be the pioneers of using sustainable energies.
Their experience may be used for helping the developing countries. In the
international communication, people ought to appreciate the pioneer’s contribution to
push the progress of using sustainable energies.
A well-developed international society ought to have the long-term plan: (1) to
help all member countries gradually to have a good existence condition; (2) to
develop the sustainable energy technology as fast as possible; (3) to save valuable
clean gas energy as much as possible. The United Nations ought to help people to set
up the scientific perspective view to solve the vigorous competition for limited fossil
energy resources.
Further, the nuclear fusion power station will be growing forward, and the gas
energy will be replaced by the nuclear fusion power and the sustainable energies at the
end of this century or early of next century.

10 Starting from NGH: What Can We Do Further?


It is great for the intelligent people before to carry out the exploitation practice,
they have done quite a lot of theoretical studies on NGH, which provide us many
possibilities in practice to use the properties of NGH to develop a series of new
possible processes.
People can master the technologies both of NGH formation and dissociation,
starting from the studies on the NGH’s properties. Not only the technologies on NGH
exploitation and gas storage and transportation, but also other NGH related
technologies could be developed, when the processes of NGH formation and
dissociation are well controlled. Here we will provide a few examples as follows:
(1) Purifying and enriching CBG from 60 70% to 85 90%, by NGH formation;
(2) Recovering or separating C1 C3 fractions from petroleum refining gas as raw
materials of chemical industry, by NGH formation;
(3) Producing industrial hydrogen from coke oven gas, in which the hydrogen
content from 57% approach to 80-85%, by NGH formation;
(4) Recovering or separating the C2 C4 fractions from natural gas as raw materials
of petrochemical industry, by NGH formation [41,42];
(5) Using NGH instead of gasoline and diesel fuel to reduce the fuel fee around 30 
50%;
(6) Using NGH formation system instead of whole set of deep chilling system for
LNG receiving station to keep the low temperature;
(7) Producing pure water from seawater [43-46] or developing new low temperature
cyclic process [16,46] by alternately forming and dissociating NGH;
(8) Using LNG or NGH as chilling source for air separation, dry ice crystal making
or steam pyrolysis gas separation etc.;
(9) Reducing green house gas expelling to help the environment protection, by CO2
hydrate formation [48-50];
(10) Using hydrate to transport the poison product, chlorine gas [47].
Above listed processes are those of initial ideas based on the basic properties of
NGH, but not being realized. Anyhow, it provides scientists wide fields to develop
new processes for making best uses of valuable clean gas energy.

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