Petroleum Refinery Lec.

10

Natural Gas Refining Processes

Natural gas processing begins at the wellhead. The composition of the raw natural gas extracted from
producing wells depends on the type, depth, and location of the underground deposit and the geology
of the area.

A schematic process flow diagram for Natural gas refining is shown below.

A schematic process flow diagram for Natural gas refining

The stages in the Production of Pipeline-Quality Natural Gas and NGLs are as the following:

A) Separation of Oil using Gas-Oil Separators

In many instances pressure relief at the wellhead will cause a natural separation of gas from oil (using a
conventional closed tank, where gravity separates the gas hydrocarbons from the heavier oil). In some
cases, however, a multi-stage gas-oil separation process is needed to separate the gas stream from the
crude oil. These gas-oil separators are commonly closed cylindrical shells, horizontally mounted with
inlets at one end, an outlet at the top for removal of gas, and an outlet at the bottom for removal of
oil. Separation is accomplished by alternately heating and cooling (by compression) the flow stream
through multiple steps. Some water and condensate, if present, will also be extracted as the process
proceeds.

Gas-Oil Separator

B) Removing of condensate using Condensate Separator

Condensates are most often removed from the gas stream at the wellhead through the use of
mechanical separators. In most instances, the gas flow into the separator comes directly from the
wellhead, since the gas-oil separation process is not needed. The gas stream enters the processing plant
at high pressure (600 pounds per square inch gauge (psig) or greater) through an inlet slug catcher
where free water is removed from the gas, after which it is directed to a condensate separator.
Extracted condensate is routed to on-site storage tanks.

C) Dehydration

A dehydration process is needed to eliminate water which may cause the formation of hydrates.
Hydrates form when a gas or liquid containing free water experiences specific temperature/pressure
conditions. Dehydration is the removal of this water from the produced natural gas and is accomplished
by several methods. Among these is the use of ethylene glycol (glycol injection) systems as an
absorption* mechanism to remove water and other solids from the gas stream. Alternatively,
adsorption* dehydration may be used, utilizing dry-bed dehydrators towers, which contain desiccants
such as silica gel and activated alumina, to perform the extraction.

Note: (Adsorption is the binding of molecules or particles to the surface of a material, while absorption
is the filling of the pores in a solid). The binding to the surface is usually weak with adsorption, and
therefore, usually easily reversible.
D) Contaminant Removal

Removal of contaminates includes the elimination of (hydrogen sulfide, carbon dioxide, water vapor,
helium, and oxygen).

In addition to water and oil removal, one of the most important parts of gas processing involves the
removal of sulfur and carbon dioxide. Natural gas from some wells contains significant amounts of
sulfur and carbon dioxide. This natural gas, because of the rotten smell provided by its sulfur content, is
commonly called ‘sour gas’. Sour gas is undesirable because the sulfur compounds it contains can be
extremely harmful, even lethal, to breathe. Sour gas can also be extremely corrosive. In addition, the
sulfur that exists in the natural gas stream can be extracted and marketed on its own.

Sulfur exists in natural gas as hydrogen sulfide (H2S), and the gas is usually considered sour if the
hydrogen sulfide content exceeds 5.7 milligrams of H2S per cubic meter of natural gas. The process for
removing hydrogen sulfide from sour gas is commonly referred to as ‘sweetening’ the gas.

I. Conventional Natural Gas Sweetening

The primary process for sweetening sour natural gas is quite similar to the processes of glycol
dehydration. Unfortunately, there is no one solvent that has all the desirable characteristics and best
suited for treating the particular sour gas. The main solvents used in gas sweetening are shown in the
table below.

On the other hand, the sour natural gas mixtures vary in:

 H2S and CO2 content and ratio

 content of heavy or aromatic compounds

 content of COS, CS2, and mercaptans

Most of the regenerative chemical sweetening solvents are alkanolamines. These compounds combine
chemically with the acid gases in the contactor to form unstable salts. The salts break down under the
elevated temperature and low pressure in the still.

When amine solutions are used to remove the hydrogen sulfide. This process is known simply as the
‘amine process’.

There are two principle amine solutions used, monoethanolamine (MEA) and diethanolamine (DEA).

Recent studies have shown that MDEA has commercial advantages over other amines. It is less corrosive
to carbon steel and the solution is stable and not as susceptible to degradation. Concentrations of up to
50% can be used without damaging process equipment. Also, MDEA-based processes are simple with
lower capital and maintenance costs.

MDEA is known, however, for its low ability to absorb carbonyl sulfide (COS) and mercaptans. This
disadvantage can be overcome by mixing MDEA with secondary amines, such as DEA for increasing the
mixture reaction rates with these sulfur and mercaptan compounds.

In general the limitations of amines are : H2s emissions, amine is easily contaminated, corrosion from
amine degradation, complex operation, high initial capital cost.

The amine solution used can be regenerated (that is, the absorbed sulfur is removed), allowing it to be
reused to treat more sour gas.
RNH2 + H2S = RNH3HS

RNH2 + H2O + CO2 = RNH3HCO3

where R = C2H4OH

Amin absorber

Economics of Gas Sweetening

In process economics, the total expenses on capital (capex) and operation (opex) of a plant are directly
influenced by the design and operating parameters of the process. The circulation rate is considered
the most important influence on the economics of gas treating with chemical solvents. Solvent
circulation rate influences the size of pumps, lines, heat exchangers, and regeneration tower, and
affects the capital cost of gas-treating plants. Circulation rates also influence the energy requirement for
solvent regeneration because the reboiler heat duty is associated directly with the liquid rate.

Mol loadings (moles of acid gas picked up in the contactor per mole of solvent circulated) are generally
in the range of 0.25 to 0.33 moles acid gas per mol of MEA.

Another factor that plays an important role in gas-treating economics is solution corrosivity, which
determines the material of construction of units due to the high temperatures and solution acidity.
II. Hot Potassium Carbonate Solution

Another chemical solvent, potassium carbonate (K2CO3), has also been used for removing H2S and
CO2 from manufactured or natural gas. It is not widely accepted in the sour natural gas industry, but it is
periodically mentioned in the literature as finding some application under specific conditions. It requires
lower heat input for regeneration and is therefore somewhat less costly to operate than some amine
processes. Also, no heat exchanger is required in the regeneration equipment. The process has
difficulty in meeting the H2S specification of the treated gas if the H2S/CO2 ratio is not extremely small.
This process is significant for treating gas with a large concentration of CO2.

Natural gas sweetening unit using Hot Potassium Carbonate

E) Nitrogen Extraction

Once the hydrogen sulfide and carbon dioxide are processed to acceptable levels, the stream is routed
to a Nitrogen Rejection Unit (NRU), where it is further dehydrated using molecular sieve beds. In the
NRU, the gas stream is routed through a series of passes through a column and a brazed aluminum plate
fin heat exchanger. Using thermodynamics, the nitrogen is cryogenically separated and vented. Another
type of NRU unit separates methane and heavier hydrocarbons from nitrogen using an absorbent*
solvent. The absorbed methane and heavier hydrocarbons are flashed off from the solvent by reducing
the pressure on the processing stream in multiple gas decompression steps. The liquid from the flash
regeneration step is returned to the top of the methane absorber as lean solvent. Helium, if any, can be
extracted from the gas stream in a Pressure Swing Adsorption (PSA) unit.

F) Methane Separation (NGL Extraction): The process of demethanizing the gas stream can occur as a
separate operation in the gas plant or as part of the NRU operation. Cryogenic processing and
absorption methods are some of the ways to separate methane from NGLs. The cryogenic method is
better at extraction of the lighter liquids, such as ethane, than is the alternative absorption method.
Essentially, cryogenic processing consists of lowering the temperature of the gas stream to around -
120 degrees Fahrenheit. While there are several ways to perform this function the turbo expander
process is most effective, using external refrigerants to chill the gas stream. The quick drop in
temperature that the expander is capable of producing condenses the hydrocarbons in the gas stream,
but maintains methane in its gaseous form.

Natural Gas in mobile applications

Natural gas both liquid (LNG) and compressed (CNG) forms is emerging as an alternative to diesel fuel.

The fuel has a number of reported advantages over diesel or gasoline fuels in transportation
applications. Not only is it in abundant supply, but also vehicles running on natural gas have lower
operating costs and reduced greenhouse gas emissions compared with their diesel counterparts.

Liquefied Natural Gas (LNG)

Liquefied natural gas is natural gas that has been converted to liquid form for ease of storage or
transport. To convert it to a liquid form, it must be cooled to minus −161.5 °C. LNG is produced from
natural gas by compression and subsequent cooling. During liquefying natural gas shrinks in volume to
about 600 times. LNG is stored in special cryogen tanks constructed as Dewar’s vessels. LNG is
transported by special marine vessels – gas carriers, equipped with cryogen tanks, and special trucks. It
is used as a lower-emission fuel for ships, trucks, buses and trains in various countries like USA, China,
South America, Iran, Pakistan. Australia and Europe. However it has higher cost of production and
storage compared to Compressed natural gas (CNG).

Compressed Natural gas (CNG)

Compressed Natural gas is made by compression the natural gas to less than 1% of the volume at
standard atmospheric pressure. It is stored in hard cylindrical containers at a pressure of 200-280 bars.