NATURAL GAS ENGINEERING

Gas Expansion – JOULE THOMSAN COOLING

When gases expand into seperators or at wellheads, the temperature drops. Frequently, such a
drop in temperature brings a gas into hydrate region. Figure gives cooling curve for a 0.6 gravity
gas. Given a gas at initial temperature and pressure that is to be expanded to a lower pressure,
one often needs to know if the expansion can cause hydrates to form. A hydrate formation
temperature- pressure curve can be plotted on a diagram. Figure to determine where it meets
the Joule- Thomsan cooling curve for the initial conditions. The point of intersection gives the
maximum expansion the gas can undergo without risking hydrate formations.

Joule-Thomson Experiment: The apparatus itself is quite simple. Imagine a tube with a porous
plate separating it into two parts. The porous plate will allow a gas to go through it, but only
slowly. It acts as a throttle. On each side of the plate there is a piston that fits the tube tightly.
Each piston can (in principle) be pushed up against the porous plate. The tube itself is insulated
so that no heat can enter or leave the
tube. The experiment is also quite
simple. Imagine that some gas is
placed between the porous plate and
the piston on the left side of the tube.
This is side 1. On the other side the
piston is flush against the porous
plate. This is side 2. The initial volume
of gas on side 1 is V1. The pressure is
p1 and the temperature T1. Now
during the experiment gas is pushed
through the porous plate by pushing on the piston on the left side. At the same time the piston
on the right side is pulled in such a way that the pressure on the right side is always p2. At the
end of the experiment all of the gas has been pushed through the porous plate. The volume on
side 1 is zero. The final volume on the right side (side 2) is V2, the pressure is p2 and the
temperature T2. The curious result of this experiment is that careful measurement shows that
T2 is not equal to T1. Under some conditions it is higher, under others it is lower.
Conclusions: First, since µ JT is positive at low temperatures and negative at high temperatures,
it must have an inversion temperature. Second, the effect seems to depend (as we expected)
on the attractive and repulsive forces acting between molecules. At low temperatures the
attractive forces predominate. At high temperatures the repulsive forces predominate. So the
Joule-Thomson effect can be explained this way: At low temperatures the intermolecular
attraction is the most important interaction. When the cold gas is expanded, the average
distance between molecules is increased. This means that the molecules are pulled apart. Since
they attract each other this takes energy. And since the process is adiabatic, the only source of
energy is the internal energy of the gas itself. So, with the internal energy reduced, the gas
cools. On the other hand, at high enough temperatures the predominant interaction is
repulsion. The gas wants to separate. It wants to expand. When it does expand energy is
obtained as the molecules separate. This increases the internal energy of the gas. And the gas
heats.
Sampling and Analysis of gas and liquid hydrocarbons:
Early gas and liquid analyses were made by low-temperature distillation on a fractionor, which
separated the hydrocarbons by boiling point. Columns were devised by W.L. Podbielniak to be
efficient and semiautomatic in their operation. The successor analytical device was a mass
spectrometer. In this device the numbers of molecular fragments occurring at various masses
were counted. By 1960 the chromatographic device became normal analytical tool for both
hydrocarbon gases and liquids. On occasion distillation analyses are still made, especially for
high boiling liquids. On AGA project distillations were made on pipeline condensates and
absorption plant absorber oils.

CHROMATOGRAPHIC ANALYSIS:
Chromatographic analysis is much better than earlier methods. It can have a more complete
separation of the constituents, a smaller size and a shorter test time. In the AGA project
extended chromatographic analyses were made on heavy hydrocarbons out to part per million.
ASTM published standards for gas, liquid, thin- layer, and steric exclusion chromatography. The
central feature is packed flow tube in which a separation of the constituents takes place based
on boiling points. A carrier gas often helium, flows through the tube continuously and exits to
detectors devices based on thermal conductivity or flame ionization. The tube frequently is as
long as 20 ft and it is in an oven for temperature control. Programmed temperature rises may
be used in the oven. Small samples are introduced with the needle piercing a septum. A 1cc gas
sample is typical. The carrier gas distributes the sample on the substrate covering the solid
packing by both absorption and adsorption. The more volatile components advance through
the column faster and arrive at detector. The arrival sequence and amounts of signal generated
prove the analysis. Two types of detectors are used. One is TCD, which indicated the change in
thermal conductivity of gas stream. The other is FID, in which separated gas is burned in air
hydrogen flame.

Analyses for H₂S and CO₂:

Since H₂S and CO₂ are soluble in water, great care is needed to bring samples into laboratory
without losing some. Field tests are quite common. H₂S is very poisonous and reactive. Its unit
of content in gas is grain per 100 standard cubic feet of gas; less than ¼ grain is normal
specification.
CO₂ is included in chromatographic analyses and may also be measured by adsorption in caustic
solution in an Orsatt pipette. A concern is to avoid absorption in water in transit or transfer.
Natural gas storage:
Natural gas, like many other commodities, can be stored for an indefinite period of time in
natural gas storage facilities for later consumption. Characteristics of underground storage
facilities need to be defined and measured. A number of volumetric measures have been put in
place for that purpose:
Total gas storage capacity: It is the maximum volume of natural gas that can be stored at the
storage facility. It is determined by several physical factors such as the reservoir volume, and
also on the operating procedures and engineering methods used.
Total gas in storage: It is the total volume of gas in storage at the facility at a particular time.
Base gas (also referred to as cushion gas): It is the volume of gas that is intended as permanent
inventory in a storage reservoir to maintain adequate pressure and deliverability rates
throughout the withdrawal season.
Working gas capacity: It is the total gas storage capacity minus the base gas.
Working gas: It is the total gas in storage minus the base gas. Working gas is the volume of gas
available to the market place at a particular time.
Physically unrecoverable gas: The amount of gas that becomes permanently embedded in the
formation of the storage facility and that can never be extracted.
Cycling rate: It is the average number of times a reservoir’s working gas volume can be turned
over during a specific period of time. Typically the period of time used is one year.
Deliverability: It is a measure of the amount of gas that can be delivered (withdrawn) from a
storage facility on a daily basis. It is also referred to as the deliverability rate, withdrawal rate,
or withdrawal capacity and is usually expressed in terms of millions of cubic feet of gas per day
(MMcf/day) that can be delivered.
Injection capacity (or rate): It is the amount of gas that can be injected into a storage facility on
a daily basis. It can be thought of as the complement of the deliverability. Injection rate is also
typically measured in millions of cubic feet of gas that can be delivered per day (MMcf/day).
The measurements above are not fixed for a given storage facility. For example, deliverability
depends on several factors including the amount of gas in the reservoir and the pressure etc.
Generally, a storage facility’s deliverability rate varies directly with the total amount of gas in
the reservoir. It is at its highest when the reservoir is full and declines as gas is withdrawn. The
injection capacity of a storage facility is also variable and depends on factors similar to those
that affect deliverability. The injection rate varies inversely with the total amount of gas in
storage. It is at its highest when the reservoir is nearly empty and declines as more gas is
injected. The storage facility operator may also change operational parameters. This would
allow, for example, the storage capacity maximum to be increased, the withdrawal of base gas
during very high demand or reclassifying base gas to working gas if technological advances or
engineering procedures allow.
Pipeline Corrosion
Unprotected pipelines, whether buried in the ground, exposed to the atmosphere, or
submerged in water, are susceptible to corrosion. Without proper maintenance, every pipeline
system will eventually deteriorate. Corrosion can weaken the structural integrity of a pipeline
and make it an unsafe vehicle for transporting potentially hazardous materials. However,
technology exists to extend pipeline structural life indefinitely if applied correctly and
maintained consistently.
How Do We Control Pipeline Corrosion?
Four common methods used to control corrosion on pipelines are protective coatings and
linings, cathodic protection, materials selection, and inhibitors. Coatings and linings are
principal tools for defending against corrosion. They are often applied in conjunction with
cathodic protection systems to provide the most cost-effective protection for pipelines.
 Cathodic protection (CP) is a technology that uses direct
electrical current to counteract the normal external
corrosion of a metal pipeline. CP is used where all or part
of a pipeline is buried underground or submerged in
water. On new pipelines, CP can help prevent corrosion
from starting; on existing pipelines; CP can help stop
existing corrosion from getting worse.

 Materials selection refers to the selection and use of corrosion-resistant materials such as
stainless steels, plastics, and special alloys to enhance the life span of a structure such as a
pipeline. Materials selection personnel must consider the desired life span of the structure as
well as the environment in which the structure will exist. Corrosion inhibitors are substances
that, when added to a particular environment, decrease the rate of attack of that environment
on a material such as metal or steel reinforced concrete.

 Corrosion inhibitors can extend the life of pipelines, prevent system shutdowns and failures,
and avoid product contamination.
Evaluating the environment in which a pipeline is or will be located is very important to
corrosion control, no matter which method or combination of methods is used. Modifying the
environment immediately surrounding a pipeline, such as reducing moisture or improving
drainage, can be a simple and effective way to reduce the potential for corrosion.
What Is the Solution?
Corrosion control is an ongoing, dynamic process. The keys to effective corrosion control of
pipelines are quality design and installation of equipment, use of proper technologies, and
ongoing maintenance and monitoring by trained professionals. An effective maintenance and
monitoring program can be an operator’s best insurance against preventable corrosion-related
problems. Effective corrosion control can extend the useful life of all pipelines. The increased
risk of pipeline failure far outweighs the costs associated with installing, monitoring, and
maintaining corrosion control systems. Preventing pipelines from deteriorating and failing will
save money, preserve the environment, and protect public safety.
Natural gas odorization and methods to odorize natural gas:
An odorizer is a device that adds an odorant to a gas. The most common type is one that adds a
mercaptan liquid into natural gas distribution systems so that leaks can be readily detected.
Other types have been used for carbon dioxide fire extinguishers.
Natural gas odorizers run the gamut from a simple wick in a container to computerized
equipment, which controls the amount of odorant based on flow rate, tracks the amount of
odorant in inventory, and alarms when odorant is not being injected into the gas stream.
Odorants used for natural gas vary from country to country, depending on gas distribution
regulations. Some odorants contain sulfur, which is oxidized to sulfur dioxide when the gas is
burned.
Sulfur containing odorants include:
tert-Butylthiol (TBM) the main ingredient in many gas odorant blends
Tetrahydrothiophene (THT), used as an odorant for natural gas, usually in mixtures containing
tert-butylthiol
2-Propanethiol, commonly known as isopropyl mercaptan (IPM) is used as an odorant for
natural gas usually in mixtures containing tert-butylthiol
Ethanethiol (EM), commonly known as ethyl mercaptan is used in Liquefied petroleum gas
(LPG), and resembles odor of leeks, onions, durian, or cooked cabbage
Dimethyl sulfide (DMS), a component of the smell produced from cooking of certain
vegetables, notably maize, cabbage, beetroot, and seafoods
Non-sulfur containing odorants include:
Methyl acrylate (MA)
Ethyl acrylate (EA)
Methylethyl pyrazine, odor of various foods including coffee and wines
Gas condensate fields:
Gas condensate fields is a single subsurface accumulation of gaseous hydrocarbons including
gasoline and kerosene vapors and, less frequently, components with a higher molecular weight.
In case of isothermal reduction of the formation pressure, part of them condenses in the form
of gas condensate. Gas condensate reservoirs can be confined in any traps and catchers.
According to the source of liquid hydrocarbons, there are the following gas condensate
reservoirs:
 primary gas condensate reservoirs formed at the depths of over 3.5 thousand meters
separate from oil accumulations;
 secondary gas condensate reservoirs formed through partial vaporization of the oil
blend.
There are saturated (the formation pressure is equal to the pressure of initial condensation)
and non-saturated (the initial condensation pressure is lower than the formation pressure) gas
condensate fields according to thermo-baric conditions.