Gas Plant 2

Eni Corporate University
G R O U P
TRAINING PROGRAM
MINISTRY OF OIL OF IRAQ
JUNIOR PRODUCTION ENGINEER
GAS PLANTS 2
Lecturer: Eng. Romano Bianco
BOOKLET N° 2
Code: IMG017-E-A0 Rev.: 02 Date : 30/07/2004 Pages number: 94

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GENERAL INDEX
1 NATURAL GAS BOOKLET N° 1
2 NATURAL GAS PROCESSING BOOKLET N° 1
3 SURFACE WELL EQUIPMENTS BOOKLET N° 1
4 COLLECTION AND TREATMENT CENTRE BOOKLET N° 1
5 TREATMENT LINE BOOKLET N° 2
6 GLYCOL DEHYDRATION SYSTEM BOOKLET N° 2
7 COOLING TREATMENT PLANTS BOOKLET N° 2
8 SOLID BED NATURAL GASOLINE PLANT BOOKLET N° 2
9 LPG PLANT BOOKLET N° 2
10 PROPANE DEHYDRATION BOOKLET N° 2
11 COS TREATING BOOKLET N° 2
12 MERCAPTAN TREATING BOOKLET N° 2
13 SWEETENING BOOKLET N° 2
14 SULPHUR RECOVERY PLANT BOOKLET N° 2
15 TAIL GAS TREATMENT BOOKLET N° 2
16 COMPRESSION UNITS BOOKLET N° 3
17 DEHYDRATION BY SOLID BEDS BOOKLET N° 3
18 SOUR WATER STRIPPER PLANT BOOKLET N° 3
19 FLARE SYSTEM BOOKLET N° 3

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20 NITROGEN PRODUCTION BOOKLET N° 3
21 COMPRESSED AND INSTRUMENT AIR

SYSTEM BOOKLET N° 3
22 FUEL GAS SYSTEM BOOKLET N° 3
23 WATER TREATMENT SYSTEM BOOKLET N° 3
24 FIRE FIGHTING SYSTEM BOOKLET N° 3
25 POWER SUPPLY SYSTEM BOOKLET N° 3
26 ALARM AND SHUT-DOWN SYSTEMS IN GAS PLANT

BOOKLET N° 3
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BOOKLET INDEX
5 TREATMENT LINE 6
5.1 GENERAL 6
6 GLYCOL DEHYDRATION SYSTEM 7
6.1 GENERAL 7
6.2 SCHEME AND FUNCTIONING 7
6.3 STRUCTURE AND FUNCTIONING OF: 12

6.3.1 Dehydration column 12
6.3.2 Circulation pumps 15
6.3.3 Calculation of the glycol flow 17
6.3.4 Regeneration 20
6.3.5 Vacuum glycol regenerators 24
6.3.6 Heat exchangers 27
6.4 OPERATION 27
7. COOLING TREATMENT PLANTS 28
7.1 GENERAL 28
7.1.1 Cooling by expansion (Joule-Thomson effect) 28
7.1.2 Operation 35
7.2 LIQUID HYDROCARBON RECOVERY BY MEANS OF COOLING 36

7.3.1 Refrigerants 40
7.3.2 Compressor 42
7.3.3 Condenser 42
7.3.4 Evaporator 43
7.3.5 Economizer. 43
7.3.6 Stabilizer column 46
7.3.7 Operation 48
8. SOLID BED NATURAL GASOLINE PLANT 49
8.1 GENERAL 49

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8.3 STRUCTURE AND FUNCTIONING OF: 53

8.3.1 Adsorbers 53
8.3.2 Air Coolers 55
8.3.3 Filters 55
9. LPG PLANT 57
10 PROPANE DEHYDRATION 62
10.1 GENERAL 62
11 COS TREATING 64
11.1 GENERAL 64
12 MERCAPTAN TREATING 67
12.1 GENERAL 67
13 SWEETENING 69
13.2 DESCRIPTION AND FUNCTIONING OF: 79

13.2.1 Absorption Column 79
13.2.2 Gas Scrubber 79
13.2.3 Regeneration Column 80
13.2.4 Re-boiler 80
13.2.5 Reflux Drum 81
13.2.6 Operation 81
14. SULPHUR RECOVERY PLANT 88
14.1 SCHEME AND FUNCTIONING CLAUS PROCESS 88
15 TAIL GAS TREATMENT 93
15.1 GENERAL 93
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5 TREATMENT LINE
5.1 GENERAL
After having undergone temporary treatments, the natural gas is delivered
from the production wells to the gas treating centre where it is processed to
meet the users’ specifications.
In general, the natural gas has to be processed to eliminate or reduce the
content of the following constituents.
1. Reducing water through:
- Dehydration with liquid absorbents
- Dehydration with solid adsorbents
- Dehydration through cooling expansion
2. Reducing the content of heavier hydrocarbons through:
- Adsorption
- Cooling and heavier hydrocarbons recovery
3. Reducing the content of hydrogen sulphide and carbon dioxide
through:
- Sweetening
These treatments are carried out by the use of the correct type of process
units, according also to the natural gas composition as described below.
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6 GLYCOL DEHYDRATION SYSTEM
6.1 GENERAL
The dehydration of natural gas to meet the water dew point specification, is
usually obtained by glycol absorption.
The glycol unit is the most commonly used dehydration system for gas
treating, since it is practical and easy to operate.
The type of glycol can be di-ethylene glycol (DEG) or tri-ethylene glycol
(TEG).
The glycol units can have two types of configurations:
- Closed circuit systems.
- Open circuit systems.
In the first configuration, the contactor is connected to its regeneration
system only.
It is a “rigid” system, as the plant has to be stopped in case the regenerator
has some problem.
In the open circuit configuration, on the contrary, there are two or more
regenerators common to all the contactors. This is a more commonly used
solution and compared to the first configuration, it allows a more flexible
operation.
This system requires only the installation of two tanks, one for the storage
of the exhausted glycol and the other for the storage of the regenerated
glycol. (Fig. 6.1, 6.2, 6.3).
6.2 SCHEME AND FUNCTIONING

The glycol plant is composed of:
a) An absorption column; called also contactor
b) A regenerator, composed of:
- Flash Drum
- Re-boiler;
- Distillation tower with reflux;
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- Filters;
- Glycol circulation pumps.
The wet gas enters into the bottom of the absorption tower, and flows
upwards through a certain number of trays, usually valve type or bubble cap
type. Regenerated glycol is circulated by means of a pumping system at the
top of the contactor and flows downwards.
The gas flows through the trays and bubbles through the glycol, that
removes by absorption the water contained in the gas.
Gas flows from one tray to another, up to the top of the contactor, while the
glycol is collected in the bottom of the absorber, diluted due to the amount
of water removed from the gas. The diluted glycol stream is called RICH
GLYCOL (rich in water).
The level of glycol in the tower bottom, is maintained by a level controller

that operates a control valve on the rich glycol outlet line.
The gas coming out from the top of the absorber is dehydrated at the
required water dew point.
The rich glycol from the bottom of the contactor, is sent to storage, and then
to the regenerator where, at a high temperature, it is re-concentrated.
The regenerated glycol stream is called also Lean Glycol.
The lean glycol is then pumped to the regenerated glycol tank and, from
there, is pumped again to the top of the contactor. (Fig.6.1)
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Figure 6.1 – Glycol dehydration plant Open circuit with Rich and Lean Glycol Tanks
Conceptual flow sheet
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Fig. 6.2 - Gas Dehydration Unit - Closed circuit alternative

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Fig. 6.3 Gas dehydration and Dew Point Control Process Flow Diagram
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6.3 STRUCTURE AND FUNCTIONING OF:
6.3.1 Dehydration column

Water is eliminated from the gas stream in the dehydration column, which is
composed of the following elements (Fig. 6.4).
• A separator at its bottom, whose task is to remove any liquid phase from
gas, mainly liquid hydrocarbons that could cause foaming in the upper
part of the contactor.
• A chimney tray, is located between the bottom separator and the
absorbing upper section. It collects the rich glycol so that it does not mix
with the liquids collected in the bottom separator.
• The upper part of the column is used for water absorption by the lean
glycol. This section is equipped with trays, bubble cap or valve type, or
with a packing, random or structured type.
Sometimes, in the small units, a gas/glycol heat exchanger coil is located
above the top tray to ensure the cooling of the lean glycol entering the
column.
In the top of the column, there is demister (a mist eliminator) whose function
is to limit the loss of glycol due to gas carry-over.
The volumes of the bottom and head sections depend on the amount of
circulating liquid and on the flow rate of the gas. The height of the upper
section of the contactor is determined by the number of trays or the packing
height.
Usually, with a gas speed within the column of 0,20-0,30 m/sec, the
distance between the trays is of 0,60-0,80 m.
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Figure 6.4 – Dehydration column with bubble cap trays

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Bubbling cap or valve trays

The number of trays depends on the operating temperature, gas flow rate
and the dew point required.
Usually, the absorbers have from 4 to 12 trays.
With regard to the bubble cap tray, each tray is composed of a punched
plate with bells mounted on the holes with risers (Fig. 6.5) and with slots in
the peripheral wall of each bell, located so as to drive the gas through the
glycol, whose level on the tray is maintained by the weirs.
The glycol flows across each tray and, passes to the outlet weir, and goes
to the lower tray. The rich glycol is collected on the chimney tray.
Inside each bubble cap the direct contact between glycol and gas takes
place.
Figure 6.5 – Bubble cap Tray

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6.3.2 Circulation pumps

The lean glycol circulation pumps are usually reciprocating type, due to the
rather high delivery pressure (the glycol is sent to the contactor top ) and
the relatively low flow rate.
There is a system of pumps, as a minimum one in operation and one on
stand-by, to take lean glycol from the storage tank and the top of the
contactor.
The rich glycol goes to the downstream parts of the unit, driven by the
pressure in the column itself.
Normally, the reciprocating circulation pumps are driven by electric motors
and have more than one pumping head, provided with an adjustable stroke
system. (Fig. 6.6a, 6.6b, 6.7, 6.8)
Fig. 6.6a Reciprocating pump

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Fig. 6.6b Reciprocating Pump dimensions and performance data
Fig.6.7 - Reciprocating pump

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Fig. 6.8 Typical reciprocating pump unit
6.3.3 Calculation of the glycol flow

Using the diagram of Fig. 6.9, for the known pressure and temperature of
the gas saturated with water, it is possible to calculate the amount of water
contained. Since a usually required water dew point is -12 °C at the
operating pressure, that gives a typical content of water equal to 50
mg/Nm3, it is possible to obtain the amount of water that needs to be
removed in the glycol unit.
For example: If the gas is water saturated at a pressure of 60 bar and a
temperature of 15 °C and the gas flow rate is 1,000,000 Nm3/d, the required
information is how much glycol needs to be circulated in order to have a
dew point of -12 °C at 60 bar.
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From the diagram, it can be seen that at 60 bar and a temperature of 15 °C,
saturated gas contains about 300 g/1,000 Nm3, of water, therefore:
Water content = 300x1.000.000/1000= 300.000 g/d = 300 Kg/d of water.
From the same diagram: at -12 °C and 60 bar the saturation water content
is around 50g/1,000 m3 therefore:
Water content, at required gas flow rate, is 0 50x1.000.000/1.000= 50.000

g/d = 50 Kg/d
The difference gives the amount of water to be removed by glycol
dehydration, i.e.:
300 - 50 = 250 Kg/d of water
Experimental data shows that, in order to eliminate 1 Kg of water, 25 Kg of

glycol are needed; as a result the required capacity of the pump is:
Q= 250x25 = 6250 Kg/d of glycol
Expressed in litres: 6250/1,118= 5590 lt/d
where 1,118 is the specific weight of glycol
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Figure 8
Fig. 6.9 Water contents of natural gases with corrections for salinity and relative
density
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6.3.4 Regeneration
The glycol regeneration system can be mounted on a skid and installed far
from the absorption tower in the “fire area” of the plant.
The unit shown on Fig. 6.10 is a typical regenerator of a small unit, where
the flash drum is integral with the Lean glycol accumulator.
Figure 6.10 – Regenerator (typical arrangement for a small unit)
A more common arrangement for a high capacity dehydration unit, usually

installed in a multiple-train gas treating plant, with two or more glycol
contactors, is described below.
Rich glycol from the bottom of the absorption tower, is firstly sent to a Flash
Drum, operated at a lower pressure, e.g. 4 bar, where absorbed
hydrocarbons are released from the gas and separated as liquid by gravity.
Then the rich glycol, under automatic liquid level control in the flash drum, is
sent to a storage tank. From the storage tank, the rich, i.e diluted glycol, is
sent to the regeneration section. Firstly by means of a transfer pump,
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usually centrifugal type, it is sent to the filtering system and then to a coil
located inside the top of a distillation column, usually called a Still Column.
The purpose of the coil is to create, by cooling, a water reflux stream inside
the still column.
The heat to partially condense the vapours that flow upwards inside the still
column is transferred to the rich glycol, which at the coil outlet has a higher
temperature.
Then, the rich glycol. goes to the heat exchanger train where it is heated by
the hot regenerated glycol, and, finally, through a control valve, operated to
control the flow rate, enters the regeneration column.
The filtered and hot glycol at about 160 °C, enters the regeneration column.
Inside the column, usually, there two sections of packing elements, such as
Pall rings or equivalent, that act respectively as a rectification section, the
upper one, and stripping section, the lower one.
In the lower packed section, the water is stripped out from the glycol stream
that flows downwards and in the upper packing, the water reflux reduces
the glycol content of the upward flowing vapours, so as to reduce the glycol
losses.
The still column is usually connected by a body flange to the re-boiler,
horizontal installed above the accumulator vessel, also horizontal.
The reboiler can be heated by a fire tube system or by M.P steam.
The operating pressure is almost atmospheric and the concentration of the
regenerated glycol depends on the type of glycol and the temperature of the
re-boiler.
Typical performance data and operating temperatures are as follows:
a) With Di-ethylene Glycol (DEG) at 164 °C (maximum allowed temperature
in the re-boiler), the achieved purity is 96 % by weight (the rest is water).
b) With Tri-ethylene Glycol (TEG) at 204 °C (maximum allowed temperature
in the re-boiler), the achieved purity is 99 % by weight (the rest is water).
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The vapours leaving the top of the still column are mostly steam with other
components, which depends on the nature of gas to be dehydrated and has
come in to contact with the lean glycol in the absorber.
The temperature of the overhead vapours is around 100 °C.

The hot regenerated glycol flows from the reboiler to the heat exchanger
train, where it is cooled against the rich glycol and then, by means of
pumps, usually centrifugal type, through a final cooler either by air or water
where a temperature of 50 °C or so is reached, before being sent to the
lean glycol storage tank.
From the tank, the regenerated glycol is sent, by means of the reciprocating
pumps mentioned earlier, to the absorption tower (Contactor).
Fig. 6.11 - Glycol gas dehydration - Typical arrangement of a skid-mounted unit

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Fig. 6.12 - Glycol Storage tank system

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6.3.5 Vacuum glycol regenerators

To improve the purity of lean glycol, as the temperature cannot be
increased in the reboiler higher than the values said before, due to the
glycol decomposition at higher temperatures, so alternative, ways to reduce
the pressure of the regenerators have been adopted.
The more common systems are:
1) VACUUM PUMP (Fig. 6.13)
2) INJECTOR/EJECTOR (Fig. 6.14)
The vacuum pump is connected to the top of the still column and creates a
certain degree of vacuum in the system, still column and reboiler.
In the other solution, the ejector uses steam as power fluid.
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Figure 6.13 – Glycol regenerator with vacuum pump

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Fig. 6.14 Glycol regenerator with injector/ejector

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The improved regeneration can lead to glycol purities in the order of 99.0 wt
% for DEG and 99.6 wt % for TEG.
6.3.6 Heat exchangers

As said earlier, the temperatures of glycol, streams are very important in
both parts of the glycol unit, i.e. the absorbing section and the regeneration
section.
In the contactor the key temperature is that of the gas entering the
contactor.
Usual operating temperatures are in the order of 30 °C to 55 °C. At higher
temperatures, the glycol purity required is very high and not easily
achieved.
In addition it is always good practice to feed the lean glycol to the top of the
contactor, at a temperature close, but at least 5 C higher, than the gas
temperature to reduce the amount of heavy hydrocarbons absorbed in the
liquid glycol.
6.4 OPERATION
For the operation of the glycol units, in order to reach the required gas dew
point, the following parameters must be kept under control:
a) Flow rate of circulating glycol to the absorber.
b) Lean glycol temperature at the absorber inlet.
c) Concentration of glycol, depending on the reboiler temperature.
The proper filtering of the lean glycol stream is also an important factor in
keeping high the performance of the system.
As far as the concentration of glycol is concerned, apart from special
solutions that allows the regenerator to operate under vacuum, another
rather common solution is the one based on the use of stripping gas.
Usually, as stripping gas, fuel gas or dehydrated feed gas are used.
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The simpler way is to inject by means of a spraying device, e.g. a

perforated pipe, the stripping gas inside the re-boiler itself.
This is a simple way, but not very effective.
A better, and the only really valid way, is to install a usually small diameter ,
contact column with packing inside, on the outlet of the re-boiler.
Usually this column is between the re-boiler and the accumulator.
The regenerated glycol flows from the top of the column and the stripping
gas enters the bottom of the column.
With this arrangement, the purity of glycol can be improved significantly.
For example, in case DEG is used, the purity can reach 97-97.5 wt % and
for TEG the purity can be 99.4 wt %.
7. COOLING TREATMENT PLANTS
7.1 GENERAL
A method for the dew point reduction of a gas stream is by cooling it so as
to obtain the condensation of part of the water and the heavier
hydrocarbons, followed by the separation of the liquids.
The most common systems applied to obtain the cooling are described
below.
7.1.1 Cooling by expansion (Joule-Thomson effect)

The method is based on the behaviour of a real gas which, under most
common conditions, cools down if its pressure is reduced through a
throttling device such as a valve or a restriction orifice (Joule-Thomson
effect).
In this method, also called LTX or LTS (Low Temperature Separator)
system, after the cooling is obtained as said above, the removal of the
liquids is by gravity, in a separator located downstream of the expansion
valve.
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Functioning scheme of the system (Fig. 7.1):

The gas stream, that has to be at a rather high pressure, is pre-cooled in a
coil submerged inside the Low Temperature Separator (LTS), then flows
through a heat exchanger, where it is further cooled by the cold treated gas.
It then enters a high pressure pre-separator, and finally expanded through a
valve. Then the two-phase stream enters the separator, where the liquids
are separated by gravity from the gas phase.
The separator can be either horizontal or vertical type (Fig. 7.2, 7.3).
If the temperature required to obtain the specified dew point is rather low
and hydrates can form, the injection of an inhibitor is to be considered.
Usually, in this type of applications, glycol (DEG) is used.
In case of glycol injection upstream of the throttling valve, the aqueous
phase in the low temperature separator is a glycol–water mixture that has to
be sent to a regeneration system.
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Figure 7.1 – Dehydration through cooling by expansion

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WATER GASOLINE
DEHYDRATED GAS FROM FREE WATER
GAS OUTLET SEPARATOR AT 20°C
(PRE-COOLING COIL)
SATURATED GAS OUTLET AT 40°C
SATURATED GAS INLET AT 50°C
LIQUID AT 20 – 30 ° C
WATER GASOLINE
OUTLET OUTLET
Figure 7.2 – Horizontal low temperature separator
DEHYDRATED GAS OUTLET
(PRE_COOLING COIL)
GAS FROM FREE WATER

SEPARATOR SATURATED GAS OUTLET
GASOLINE
GASOLINE OUTLET
SATURATED GAS INLET

WATER OUTLET
WATER
Figure 7.3 – Vertical low temperature separator

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The function of the coil in the bottom of the separator, is to pre-cool the gas
stream. The gasoline, referred to also as hydrocarbon condensate, comes
out of the separator through a valve operated by the level controller that
maintains the gasoline level in the separator, while the water or the diluted
glycol comes from the lowest part of the separator, also under automatic
interface level control.
The cold vapour leaving the separator is saturated with heavier
hydrocarbons and water (in case glycol is injected upstream of the
separator, then the vapour is under saturated, because the mixing with
glycol leads to a certain degree of dehydration.).
This vapour stream from the separator is heated in the upstream heat
exchanger, exchanging heat with the inlet gas.
.The temperature of the dehydrated gas at the outlet of the heat exchanger,
is restored to a value close to ambient. After that, usually the gas is sent to
a compression station to increase the pressure up to the value required for
its transportation through a pipeline, with the correct dew point as water and
hydrocarbons.
An additional hydrocarbon recovery, through a refrigeration method is also
part of the treatment, to obtain commercially valuable products such as
condensate and LPG.
The graphics of Fig. 7.4 show quantities (expressed in percentage), referred
to the condition of each component of the liquid hydrocarbons, recovered at
a constant pressure 35 bar in the low temperature separator.
Fig. 7.5 shows the relationship between the pressure and temperature of
the gas and the gasoline recovery.
The efficiency of a dehydration unit based on cooling, greatly depends on
the temperature and pressure of the gas to be treated and in the LTS.
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Figure 7.4 - Percentage of hydrocarbons recovery in a low temperature separator
Figure 7.5 - Hydrocarbons recovery according to temperature and pressure

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Experimental data are shown in Fig. 7.6, which will allow, once temperature
and pressure, upstream of the throttling valve and the pressure in the
separator has been defined, it is possible to obtain the corresponding
values for the temperature of the separator.
The low temperature dehydrating method offers the following advantages:
- rather high liquid recovery (water and hydrocarbons). The amount of
water left in the treated gas going to the distribution pipelines, can be
adjusted by changing the pressure in the separator.
- the system is based on simple and easily automatically controlled
operations and a low number of adjustments to be made to meet the
changes in the feed gas.
- The method has low operation costs.
On the other hand, the method shows the following disadvantages, limiting
its application:
- It can be used only with high pressures at the wellhead (normally
higher than 85 bar);
A lower pressure of the well produces a decrease of the cooling
through the expansion valve, to the point that an external
refrigeration unit could be required;
- If the design does not include the re-compression unit, the
differential pressure across the throttling valve is bound and limited
by the pressure that is required for the treated gas at the beginning
of the distribution pipeline.
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-
Figure 7.6- Operating temperatures and Pressures, upstream and downstream of the
throttling valve
7.1.2 Operation
The plant operation is based on gas expansion, which causes a
temperature decrease. The pressure to temperature ratio is 3:1, that means
that to each 3 bar of pressure reduction corresponds to a 1°C decrease in
temperature.
Therefore, the pressure upstream of the expansion valve is very important
in order to get the highest decrease in gas temperature and accordingly
higher vapour condensation.
The temperature of the gas at the inlet of the expansion valve is also
important. As a matter of fact, this temperature should be in principle such
that after the expansion there is no formation of hydrates, on the other hand
if a lower temperature is required to meet the dew point specification, then
the injection of a hydrate inhibitor is to be considered.
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7.2 LIQUID HYDROCARBON RECOVERY BY MEANS OF COOLING

The condensation of heavy hydrocarbons is obtained by means of gas
cooling, obtained with a refrigerating unit.
A simplified scheme of a refrigerating unit is shown in Fig. 7.7.
Typically, a refrigerant unit includes the following parts:

• COMPRESSOR
• CONDENSER
• EXPANSION VALVE
• EVAPORATOR
Compressor can be centrifugal, screw or reciprocating type, depending on

the capacity of the refrigerant unit, i.e. high capacity ones use centrifugal
machines, intermediate capacity ones are based on screw compressors
and small units have reciprocating compressors.
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Figure 7.7 – Refrigerating unit typical process flow diagram.

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With reference to Fig. 7.7, a typical scheme is as follows
The compressor receives the cold vapour from the evaporator, where the
process gas is cooled.
At the compressor discharge, the hot gas is sent to the condenser where it
is totally liquefied, usually by means of air in air coolers exchangers or by
water in shell & tube exchangers and flows into the receiver, called also
accumulator. (not shown in the figure).
Another scheme is shown on Fig. 7.8, where the compressor is a lubricated
screw type.
In Fig. 7.11 a picture of a skid-mounted unit is shown, while Fig. 7.12 shows
a process unit with a refrigerant unit.
The main parts are:
• LUBRICATED SCREW COMPRESSOR (K – 1)
• LUBE OIL SEPARATOR (S – 2)
• CONDENSER (EA – 1)
• ACCUMULATION TANK (S – 3)
• ECONOMIZER (E – 1)
• EVAPORATOR (E – 2)
• SEPARATOR FOR THE RECOVERY OF LUBE OIL (S – 4 AND
S – 5)
• COMPRESSOR SUCTION SEPARATOR (S – 1)
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Fig. 7.8 Refrigerating Unit with economizer and lubricated screw compressor
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7.3.1 Refrigerants
Generally, the substances used as refrigerants have a low normal boiling
point.
In particular, the selection of the proper refrigerant for a specific application
has to consider a fluid with a boiling point lower than the temperature to
which the process fluid has to be cooled.
The normal boiling points, i.e. the evaporation temperature at atmospheric
pressure, of some common refrigerants are shown in the following Table 1.
REFRIGERANT CHEMICAL FORMULA BOILING POINT AT

NAME ATMOSPHERIC PRESSURE
°C
Methane R50) CH4 -160
Ethylene (R1150) CH2-CH2 -100
Propane (R290) CH3-CH2-CH3 -40
Ammonia (R717) NH3 -34
R13B1 CBrF3 -58
R22 CHCIF2 -41
R12 CCI2 F2 -30
Table 1 – Boiling points of common refrigerants.
The code starting with R in the table above is according to the classification
of refrigerants by ASHRAE (American Society of Heating, Refrigerating, and
Air-conditioning Engineers).
The most common refrigerant in petrochemical units is propane.
In the process units where very low temperatures are required, e.g. the
.LNG plants or the NGL plants, proprietary process schemes can be
applied, often based on the use of mixed refrigerant fluids. The mixed
refrigerants are defined so as to have an evaporating curve such that can fit
rather closely to the condensing curve of the process fluid to be cooled
down.
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The reason for this design feature, is that close condensing and evaporating
curves allow to have narrow temperature approaches in the main heat
exchangers, that, in turn, correspond to a high thermodynamic efficiency,
i.e. lower compression power for the refrigerant units.
Mixed refrigerants are mostly used in the LNG plants.
Fig. 7.9 Propane P-H diagram

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7.3.2 Compressor
The compressors used in the gas cooling plants can be rotary type, such as
screw type.
(Fig. 7.10)
Fig. 7.10 Propane Compressor Screw Type
7.3.3 Condenser
The condenser is where the refrigerating fluid, after compression, is totally
condensed.
These coolers can be of different types, but usually they use as a
condensing agent either air or water.
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According to the type of condensing medium, the refrigerant condenser will

be an air cooler or a shell & tube heat exchanger.
7.3.4 Evaporator
The evaporator is the heat exchanger where the process fluid is cooled
down.
Usually they are of kettle type, with the refrigerant, e.g. propane, in the shell
and the process fluid in the tubes, as shown in the picture of fig. 7.11.
In particular, the liquid refrigerant, e.g. propane, at the inlet of the
evaporator flows through a throttling valve, where the pressure is reduced
and so the refrigerant is partially vaporized and cooled at the outlet of the
valve and enters the evaporator as a two-phase cold fluid.
The refrigerant in the vaporizer is at a temperature 5 or 10 °C lower than the

temperature of the process fluid.
As a result, heat is transferred from process fluid to the refrigerant fluid
which vaporizes while the process fluid is cooled down
In the scheme shown in Figure 7.8, two evaporators are shown, one is the
process gas cooler, i.e. the main exchanger of the unit, while the other one
is called economizer and is described below.
7.3.5 Economizer.
In the scheme of Fig. 7.8, the main vaporizer is:E2, where the process fluid
is cooled down, while the other heat exchanger, E1, is a pre-cooler of the
refrigerant fluid, called also economizer, that is included to improve the
performance of the unit. In fact, in E1, the liquid refrigerant coming from the
accumulator is sub-cooled, so that the refrigerant, after the expansion valve,
enters the evaporator E1 with less vapour phase and, as a result, the flow
rate to the compressor is lower than that in the case without the
economizer.
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Of course, some vapour is going to the compressor from the economizer,

but a higher pressure so that, in total, the unit with the economizer have
lower power needs.
Fig. 7.11 Model of propane evaporator (Kettle type)
Fig. 7.12 A Skid Mounted Refrigeration Unit

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Fig. 7.13 Typical utilization of a refrigeration Unit in a process plant

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7.3.6 Stabilizer column

A product complies with a refinery sales regulations, when at 100 ° F = 38
°C its vapour pressure is lower, than the atmospheric one, so that the
vaporisation in the atmospheric storage tank is limited.
The usual required vapour pressure, denoted also as Reid Vapour Pressure
(RVP) ,shall be in the range 8-12 psia.
The stabilizer column is commonly used to obtain the required RVP for the
product, either condensate or crude oil, to be sent to the storage tanks.
The cold hydrocarbon feed enters the column either at the top, if the column
has not a condenser, or into a tray below the top, to be decided via an
optimisation study.
The liquid flows downwards inside the column, (Fig. 7.14). While
descending, it warms up, exchanging heat with the hot vapour streams that
are travelling upwards.
Besides the exchange of heat, on the trays of the column, the composition
changes take place too, so that the light ends stripped out from the bottom
e.g. ethane, propane, will go mostly in the overhead gas, while the heavier
components will go in the bottom product.
Finally, the bottom product, will be cooled and sent to storage.
In order to have high efficiency for the exchange of heat and matter, the
column has, bubble caps or packing elements such as Pall rings or
equivalent.
The tower is equipped with:
- a level regulator that operates the control valve on the bottom product
outlet line.
- a level indicator;
- a temperature controller that operates the heating medium control
valve;
a pressure regulator that operates the control valve on the column top.
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Figure 7.14 Stabilizer column

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7.3.7 Operation
For the operation of a gas treating plant, it is necessary to verify that all
parts of the unit are working regularly and in a stable manner.
In particular, the operation of the compressors have to be verified and
watched with special attention.
Some aspects of the operating conditions of a compressor must be
continuously observed .
For example, for a lubricated screw compressor the oil circuit is very
important, as it ensures the correct running of the system in terms of cooling
and sealing of the rotating parts of the machine,
It has to be kept in mind that the oil, in this type of compressor, is in contact
with the refrigerating fluid and therefore, must then be separated with a high
efficiency, at the compressor discharge in the oil separator.
On the shells of the evaporator and the economizer, the drain valves should
be periodically opened to check whether oil is present and discharge it, if it
is found, as, otherwise, it can create a film on the free side of the refrigerant
that will limit the evaporation and make the cooling capacity lower.
Usually, the temperature of the process fluid is controlled at the cooler
outlet by means of a controller that operates a valve on the vapours going
to the compressor suction.
Through this valve the pressure within the evaporator varies, increasing or
decreasing the evaporation temperature of the refrigerant and
consequently, the temperature of the process gas.
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8. SOLID BED NATURAL GASOLINE PLANT
8.1 GENERAL
The partial removal of heavier hydrocarbons from a gas stream, can be
obtained together with the removal of water through a series of separators
of proper sizes and configurations.
Technical and economic analyses could indicate different solutions to obtain
a higher recovery of heavier fractions, which often are present in the natural
gas.
This extraction process is known as stripping and requires special plants.
The reasons leading to this method are mainly economic.
Such economic reasons are essentially based on the difference between
the prospective profits that can be obtained from selling the various
hydrocarbons together with the gas and those obtainable from the separate
selling of liquid hydrocarbons and gas. Of course, the determination of such
profits is done through accurate evaluations of operation costs that must be
met in the various cases.

It is a fully automated plant (Fig. 8.1a, 8.1b), highly indicated for the
recovery processes of heavier hydrocarbons.
An additional task carried out by the plant is the gas dehydration. The
adsorbent is a standard or Sovabead, also used in the gas dehydration
plants. Its working principle is the same of the long cycle plant, with the only
difference that the first is equipped with 3 adsorber instead of 2, one of
which is cyclically used in the adsorbing process, one in the heating and the
other in the cooling process. On average, each cycle lasts about 25
minutes.
Natural Gas coming from the field with some condensate and free water, is
fed to the separators located at the plant inlet in order to separate the liquid
phases.
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The gas then proceeds to the plant separator (S1), whose task is to remove
the liquid carry-over from the gas streams. Then, the gas is sent to a FCV,
Flow Control Valve, which automatically regulates the flow-rate of the
regeneration gas. With this kind of control, the gas flow is split into two
streams:
Main Gas Stream Regeneration Gas Stream

a) The main stream goes to the adsorber (V1) containing 90% of
standard Sovabead and 10% (W) Sovabead, the latter placed in the top
part of the adsorber. The gas enters through the top, flows downwards
and leaves the bottom of the adsorber de-hydrated. and with less heavy
hydrocarbons.
The removal of heavier hydrocarbons (stripping) and water (dehydration)
are performed by means of capillary attraction through the several
superficial holes scattered all over the adsorbing material.
When the gas comes out of the plant, it is filtered by means of acyclone
gas washers and bag filters, passes through a flow meter and is sent to
the pipeline.
b) The regeneration gas stream (about 20% of the total gas), taken
upstream of the flow control valve, through the measurement flange and
the two valves (FC V 4) and (FC V 5) , enters the top of the absorber
(V2) and, flowing downwards, it cools down the Sovabead to a
temperature that is quite similar to that of the main gas stream being in
the adsorbing stage at the same time.
The operating temperature for an efficient adsorption shall be in the range

between 10 and 50 °C.
The regenerated gas had previously been pre-heated thus becoming under-
saturated. In such conditions, the gas passes through the shut-down SOV 1
and goes to the molten-salt HEATER (R1) where it is further heated to a
temperature which allows the re-generation of the adsorbing material inside
the absorber (V3) during the heating phase.
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The adsorbent material (Sovabead) is to be considered re-generated when

the temperature of the outgoing gas from (V3) has stabilized at about 275°C
for at least 5’. Before entering (V3) part of the gas is used in the stabilizer
(C1) in order to heat the hydrocarbons up to a given temperature to
accomplish its stabilization process. The three-way shut-down valve SOV1
by-passes the regeneration gas flow from the adsorber, cutting the flow
from the HEATER when:
a) Long shutdowns of the HEATER

b) Heater Flow-line and backflow failures.
The three-way-valve is also operated in case of low temperature of the gas

coming from the HEATER, which should never be under 270°C.
The gas coming out the (V3) is rich in H2O and hydrocarbons in vapour
state passes through the three-way valves FCV7 and FCV6 and enters the
exchanger E2. At this point, the gas is cooled down and reaches the same
temperature of the gas coming from the main flow. Due to this cooling,
some water and hydrocarbons will condense and are separated, in the
separator S2.
After the separation of these liquids, the gas, joins the main gas stream.
Once the cycle in the adsorbing tower is completed (V1), a timer controls
the cycle switching. After this switching process, (V1) the regenerating
process, (V2) the adsorbing process and (V3) the cooling process start.
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Figure 8.1a Solid bed stripping plant

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8.3 STRUCTURE AND FUNCTIONING OF:
8.3.1 Adsorbers
They consist of vertical columns, built with two shells. One is internal and
thin that supports the insulation placed in the gap between the inner and the
outer steel-shell, the other has proper thickness in order to withstand the
maximum operating pressure of the tower. (Fig. 8.2). The inner built
insulation layer inside the column saves heat during the regenerating
process. During each regenerating process of the dehydrators contained in
the tower, the huge steel mass of the outer shell (70 Kg/cm2) is not heated
up, because it is thermally isolated from the hot gas. Just over the lower
bottom of the tower there is an open grid that holds the adsorbent bed. In
order to avoid the dehydrating material clogging the grid, and subsequently
an increasing in flow resistance between the incoming and outgoing gas in
the tower, the bottom is fitted with a wire net covered with a larger sized
ballast than the dehydrating material.
Fig. 8.1b Solid Adsorbent System

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Fig. 8.2 Adsorber

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8.3.2 Air Coolers

They are usually made of a finned tube bundle, topped by a fan that allows
air circulation through the tube bundle, thus extracting heat to the fluids
inside the tubes. (Fig. 8.3).
From a structural point of view, the fan could also be placed under the tube
bundle, and in this case the cooler is defined FORCED CIRCULATION air
cooler, while if the fan is placed on top of the tube bundle it is called
INDUCED CIRCULATION air cooler.
The air cooler fins are located directly on the tube, where the hot fluid
circulates, so that there is a higher exchange surface with the same overall
dimensions.
The control of the process fluid outlet temperature is obtained by means of
a temperature controller that varies the pitch of the blades in the fan and
therefore the flow of cooling air to the tube bundle, or the flow of the forced
air by closing or opening some windows to allow air circulation.
8.3.3 Filters
The processed gas coming from the plant and going to the Solid Bed
Stripping plant (dry frack) is filtered through a group of filters (Fig. 8.4),
which are composed as follows:
- Grid Filter
- Cyclone Gas Washer
- Bag filter
This set of filters has the purpose of retaining the sovabead dust caused by
the breaking of this solid material due to contact with gases and to the
repeated heating-cooling processes.
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Fig. 8.3 Air cooler. Conceptual diagram
Fig. 8.4 Filters set

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9. LPG PLANT

The gas plant consists of three distillation towers connected in series.
The following description refers to one example of LPG process plant with
annexed the relevant process flow diagram. (Fig. 9.1a, 9.1b, 9.1c)
The feed gas enters the Deethanizer feed surge drum. The surge drum has
a water boot for the withdrawal of any free water that settles out. From the
feed surge drum the liquids are pumped forward, via a feed coalescer to
remove traces of free waters, and combined with the Reformer overhead
liquids before entering into the Deethanizer column. The feed Gas from the
surge drum is compressed in a two-stage compressor, with an intercooler
and also fed into the Deethanizer column. The Deethanizer column is
reboiled by LP steam in a thermosyphon re-boiler. A water draw drum
removes water that settles out in the Deethanizer column at tray 26.
Overheads from the Deethanizer are mixed with a recycled ‘Lean oil”
stream taken from the Debutanizer bottom products, and the mixture
partially condensed against cooling water before entering the overhead
accumulator drum. Liquids from the overhead accumulator are totally
refluxed into the Deethanizer column. The off-gas forms the primary source
of fuel gas for the refinery. The lean oil re-circulation is used to minimize
losses of valued LPG components into the fuel gas system.
The bottoms product from the Deethanizer flows under pressure difference
into the second column of the distillation train, the Debutanizer. The
Debutanizer is a 34-tray column also re-boiled by LP steam in a thermo-
syphon reboiler. The Debutanizer column overhead gas is condensed with
cooling water and flows into the overhead accumulator, which provides
column reflux and overheads liquid product. The overheads liquid product is
a LPG stream, i.e. contains both Propane and Butanes. The LPG stream is
fed to the LPG treater for removing the mercaptans and then enters the
third distillation column, the C3 / C4 Splitter.
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The bottoms product from the debutanizer column is stabilized light

Naphtha (LSR). This product is cooled in an air fin fan cooler and then with
cooling water before being fed to the LSR Merichem Treater section, also
for removal of mercaptans. After treatment, the LSR is routed as product
rundown into the gasoline blending pool.
The LPG stream returning from the treater section is preheated with the
Butane product and enters the 30-tray C3 / C4 Splitter column. A 150#
steam, thermo-syphon re-boiler, also re-boils this splitter column.
Overhead Propane from the splitter column is condensed against cooling
water into the overhead accumulator. Liquids from the accumulator provide
reflux for the splitter column and the finished Propane product rundown to
storage bullets.
The bottoms Butane product is first cooled against the incoming splitter
column feed, and then against cooling water before leaving the units as the
product rundown to the storage spheres.
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Fig.9.1a Process flow diagram feed drum and de-ethanizer

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Fig. 9.1b Process flow diagram debutanizer system

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Fig. 9.1c Process flow diagram debutanizer system

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10 PROPANE DEHYDRATION
10.1 GENERAL
Quite often a hydrocarbon stream needs to be separated into each
component. This process is called fractionation. The fundamental principle
for fractionation is that each component has a different boiling point .
The usual order is to remove the lighter product first. The line of treatment
starts with ethane, then propane, then butane (iso then normal) and finally
condensate.
Fractionator towers are usually named with reference to the overhead
product, e.g. a deethanizer implies that the top product is mainly C2 with a
low content of propane.
Depropanizer
The feed gas goes in the depropanizer column. This tower separates the
propane from the rest of the butane and heavier hydrocarbons. The
propane is separated from the column head and goes first, through the
condenser, to the accumulator and then with pumps towards the storage. A
fraction of the produced propane is refluxed through the pump in the head –
column. The bottoms product enters, after the heating in the reboiler, the
debutanizer column. The final step is to separate butane from condensate.
(Fig. 10.1)
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Fig. 10.1 Depropanizer and Debutanizer

Process flow diagram
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11 COS TREATING
11.1 GENERAL
Carbonyl sulphide (COS)
This substance is produced as a combination of carbon dioxide (CO2) and
hydrogen sulphide (H2S) that are present in the raw gas. Carbonyl sulphide
is present in small quantities in raw natural gas, and sometimes is produced
during the dehydration step in gas treating if the molecular sieves used are
not selected appropriately.
Carbonyl sulphide concentrate in the propane or LPG product in a natural
gas processing unit. If there is a total sulphur specification on the propane
product, carbonyl sulphide may need to be removed in order to meet the
total sulphur limitation. On the other hand, the removal of carbonyl sulphide
may be advisable because, carbonyl sulphide and water at ambient
temperature react almost quantitatively to from H2S and CO2.
H2O + COS → H2S + CO2
This reaction can be the reason why there are a number of instances where
“sweet” propane “turned sour” in storage or transport. While COS is not
itself corrosive, the hydrolysis product H2S is corrosive, especially in the
presence of water. This corrosivity is reflected in the failure of the ASTM D-
1838 copper strip corrosion test, and is thought to be a major problem in the
liquefied petroleum gas industry.
There are several processes that are used to remove the COS. This is
carried out by a two stage process which involves the hydrolysis of the COS
and the subsequent absorption of the H2S which is produced by this
reaction.
A scheme of a potassium hydroxide/Methanol process unit for removing

COS from a propane stream is shown in Fig. 11.1
The potassium hydroxide is contained in a simple vertical vessel as shown
in (Fig 11.1) and methanol is injected into the sour hydrocarbon liquid.
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Fig. 11.1 COS treating

Potassium hydroxide and methanol are consumed by the removal of COS.

Mick reports that for 7,000 barrels per day of propane containing 20 ppm
COS approximately 150 Lbs of potassium hydroxide and 100 gallons of
methanol are consumed per day.
McClure and Morrow and Weber report the use of diglycolamine (DGA) for
removing COS. The schematic flow diagram of the liquid – liquid contact
unit is shown in Fig. 11.2. The only difference in this unit and a regular
amine sweetening unit is the coalescer and water wash that must be used
to recover entrained DGA from the hydrocarbon liquid.
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Fig. 11.2 Malaprop process

Synetix reports that they have a catalytic process using their PURASPEC
products that removes COS. There are three PURASPEC catalysts which
can be used to destroy COS. Two of these (PURASPEC 2070 and
PURASPEC 2075) are capable of carrying out both the hydrolysis and
absorption reactions while one product (PURASPEC 2312) acts only as a
catalyst for the COS hydrolysis reaction. They report efficient destruction of
low levels of COS by hydrolysis with only a modest molar excess of H2O.
This process is operable over a wide temperature range and in many
gaseous process streams to cover most COS hydrolysis needs.
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12 MERCAPTAN TREATING
12.1 GENERAL
The Merox process is a catalytic process for conversion of mercaptans to

disulfides. It operates as either a mercaptan extraction process or a
sweetening process where the disulfides are removed from the
hydrocarbon. Either of these functions can be carried out independently or
in combination. When only the extraction is used, the process is referred as
Merox extraction. When operated to sweeten only (converting mercaptans
to disulfides) it is referred to as Merox sweetening. The combination
operation is applicable to all gasoline and lighter hydrocarbon materials.
The process was developed by Universal Oil Products Company. There is a
competitive process similar to Merox licensed by Merichem.
The dual method of operation is accomplished through the use of a catalyst.
The catalyst promotes direct oxidation of mercaptans to disulfides at
ambient temperature using atmospheric oxygen. When used for mercaptan
extraction the mercaptans are extracted by caustic soda. Instead of
regeneration through steam the Merox process regenerates caustic by
blowing with air. The disulfides formed by the regeneration reaction are
insoluble in the caustic and can be separated.
Fig. 12.1 shows a combination Merox process. Sour feed entering the
bottom of the mercaptan extractor flows upward in counter-current contact
with the caustic containing the Merox catalyst. Mercaptans are extracted
from the feed which flows to a caustic settler for final caustic removal. It
then-flows to the sweetening tower where it contacts more caustic
containing Merox catalyst to convert higher molecular weight mercaptans to
disulfides.
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Fig. 12.1 Schematic flow sheet for mercaptan process
Air is injected with the hydrocarbon – caustic stream entering the sweetener
to promote the conversion. From the sweetener the hydrocarbon – caustic
mixture flows to the settler tower where caustic and hydrocarbons are
separated.. The caustic containing the extracted mercaptans flows from the
bottom of the extractor tower to the caustic regenerator where it is
regenerated by air and the mercaptans are converted to disulfides. The
disulfides are insoluble in the caustic- water solution and are decanted in a
separator before the regenerated caustic is re-introduced to the mercaptan
extraction tower.
Low molecular weight hydrocarbon liquids require only extraction because
they contain negligible amounts of high molecular weight mercaptans.
Heavier stocks such as kerosene and fuel stocks require sweetening
because the disulfides, which remain in the treated stock, do not cause
problems for those products.
Merox units usually have lower operating costs than steam generated
caustic units. A Merox has trivial steam consumption, low power costs and
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no cooling costs. The 60-70% of the operating cost is the cost of the Merox
catalyst.
The mercapfing is a fixed bed liquid phase catalytic process in order to
convert mercaptans to disulfides. In mercapfing, the disulphides are not
removed but remain in the hydrocarbon stream. Conversion is
accomplished through the oxidation of the mercaptans with air. Though the
sulphur remains in the hydrocarbon, the hydrocarbon effluent from the unit
passes the copper strip corrosion test. Catalysts must be periodically
regenerated because of the plugging with oxidation products.
13 SWEETENING
Natural gas may contain high quantities of hydrogen sulphide H2S and/or
carbon dioxide CO2. The presence of these compounds renders the gas a
sour gas. This is specially because sulphur has such negative effects on the
quality of the produced gas, that the concentration of both components
have to be reduced from the gas flow before being put into the distribution
conducts for the users. The regulations allow a maximum of H2S equal to
0,002 gr./Nmc (1,31 PPM).The amount of CO2 in the gas produced will
depend in the amount required by the regulations. Typical values allow a
maximum concentration of carbon dioxide and other inerts to 4% molar of
the gas. If the content of CO2 is within these values the process selected to
remove the hydrogen sulphide has to avoid the removal of the carbon
dioxide. The necessity of a efficient natural gas sweetening process is due
to the following reasons:
- the toxicity of the hydrogen sulphide.

- sulphur dioxide is formed after the gas combustion;
- the corrosive action of sulphur compounds in metals especially with
the presence of water even under the form of steam.
- the corrosive action of carbon dioxide
- the problem of hydrogen embrittlement of the vessels containing the
gas
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- to reduce corrosion in pipelines and processing equipment

- for economic transportation of gas over long distances
Normally, the natural gas desulphurization processes can be grouped into 9

technology categories. These technology categories are as follows:
1 Chemical Solvents
2 Physical Solvents
3 Combination Chemical and Physical Solvents (Hybrids)
4 Fixed Beds (Adsorption)
5 Cryogenic Distillation
6 Membranes
7 Direct Conversion (Liquid Redox)
8 Scavenging technology
9 New Processes - Hybrid (Membrane and Amine, Liquid Redox and
Amine)
The first six are used for bulk removal of acid gas and can be tailored to a
wide range of outlet concentrations, direct conversion is used for low
amounts of H2S and scavenging is used for small throughputs or trace
removal. A combination of processes can be used to full fill particular
processing requirements.
Chemical solvent processes involve the absorption by chemical solutions at
preferably high pressure and near ambient temperature. The solvent in an
aqueous solution, bonds with the acid gas component and removes them
from the feed gas, the sour gas components are then released when the
temperature of the solvent is increased or/and the pressure is reduced.
Common chemical solvents include aqueous solutions of amines, inorganic
salts or mixtures of them. The amines more commonly used are
Monoethanolamine (MEA), Diethanolamine (DEA), Methyldiethanolamine
(MDEA) and Diglycolamine (DGA). The inorganic salts are mostly basic
carbonate solutions and caustic soda.
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In general, selection of a proper gas treating process involves consideration

of the following factors:
- Gas composition, including CO2, H2S and trace sulphur components

- Inlet pressure and temperature
- Treated gas purity specification. Avoid removing more CO2 than
required to meet specs
- Need for selectivity
- Co-absorption of hydrocarbons
- Process Capital and Operating costs including cost of solvents and their
availability
- Process royalty fees if any
- Corrosion/Metallurgy Requirements
- Process experience with similar treating requirements.
- Chemical degradation and evaporation losses
- Process support from the licenser, availability of chemicals/spares at
location
- Environmental performance, disposal of effluents
- Water content for raw and treated gas
Process Advantages and Disadvantages Chemical Solvent Process
Monoethanolamine (MEA) Process
Advantages
- High reactivity
- Low solvent cost
- Good thermal stability
- Ease of reclamation
- Low hydrocarbon content of acid gas produced
- Lower plant investment compared to other amine processes
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Disadvantages
- Inability to cope with and gas containing O2, CS2
- Will remove all the CO2
- Higher vaporization losses than DEA, MDEA
- Ineffective for removing mercaptans
- High residual acid gas concentration in lean amine
- Non-selectivity for removing H2S in the presence of CO2
- Higher utilities than hot pot and most physical solvent processes
- Most corrosive amine
- Freeze point 50oF - Transportation of 15% water solution may be
required (Freeze point 9oF)
- If gas is not saturated reverse osmosis water or equivalent is needed to
maintain amine concentration, it will re-hydrate dry gas. This is a
general point for amines.
Diethanolamine (DEA) Process
Advantages
- Resistance to degradation by COS and CS2
- Lower vaporization losses and regeneration energy required
- Less corrosive
Disadvantages
- Lower reactivity
- Higher recirculation rates
- Higher solvent costs
- In CO2 only services it will degrade and be very corrosive
- Lack of selectivity for H2S and CO2
maintain amine concentration, it will re-hydrate dry gas
- Freeze point 80oF - Transportation of 15% water solution may be
required (Freeze point 28oF)
- Difficult to reclaim - Vacuum distillation, ion exchange
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Methyldiethanolamine (MDEA)
Advantages
- High selectivity of H2S over CO2
- High acid gas loading per mole of solvent
- High solvent concentration
- Low regeneration energy
- Low solvent circulation
- Low degradation due to contaminants
- Selectivity not affected by low pressure
Disadvantages
- Higher solvent cost
- Loss of selectivity for H2S over CO2 as the concentration of H2S is
increased
- Little increase in allowable loading with increase of pressure
- Tends to be foamy due to hydrocarbon co-absorption
- Reclamation process more complicated
Diglycolamine (DGA) -Econoamine
Advantages
- High reactivity
- Solution is resistant to freezing better for cold climates
- Effective in removing RSH components
- Very high concentration solution, lower circulation rates
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Disadvantages
- Absorbs heavy or aromatic hydrocarbons (an advantage in processes
were traces of heavy hydrocarbons will cause problems i.e. Benzene
removal for LNG production)
- Proprietary process

In a chemical solvent process, the acid gas components are chemically
attached to the solvent. With chemical solvents, a CO2 rich gas can be
treated to low levels of CO2 without deep regeneration of the solvent.
However, there is a limit to the CO2 removal capacity of these solvents.
This limit is independent of CO2 partial pressure, as it is determined by
stoichiometry and corrosion prevention. The reaction rate H2S with amine is
much faster due to its higher acidity and is readily removed from the feed
gas.
Chemical solvents are most suitable for handling gases with relatively low
partial pressures of CO2 or where a very low level of CO2 in the treated gas
is required. Usually, energy requirements for chemical solvents are
relatively higher.
Most chemical solvent sweetening processes involve absorption by

chemical solutions at high pressure and at low temperature. A solvent in the
aqueous solution will react with the acid gas components to form a
complex. The solvent bonds with the acid gas components in a chemical
manner until the temperature of the solvent is increased and/or the pressure
is reduced at which time the complex is decomposed and the sour
components released.
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A sweetening plant operation on amine consists mainly of two pieces of

equipment, i.e.:
- the packed absorber or plate absorber where the gas is washed with an
absorbent;
- the distillation column (de-absorber) where the absorbed substances
(hydrogen sulphide, carbon dioxide) are separated from the absorbent
until regeneration.
With reference to the scheme, (Fig. 13.1) the gas containing hydrogen
sulphide and carbon dioxide enters the lower part of the absorption tower
whereas the aqueous amine solution enters at the top in a counter current
fashion. The sweet gas comes out of the tower top, whereas the amine rich
solution, now saturated with hydrogen sulphide and/or carbon dioxide, is
gathered at the bottom of the tower. The rich solution is warmed up the heat
contained in the regenerated solution, its pressure reduced to allow the
removal of the acid gases and then is sent to the top of a distillation tower
The rich solution is regenerated with the steam developed by the re-boiler.
After the regeneration process, the solution of amine passes, as mentioned
before in heat exchangers where it is cooled. Then it goes back into
circulation through a pump. To cool the solution to an ideal absorption
temperature, a water or air exchanger is installed between the pump and
the absorption tower. The acid gases, that is hydrogen sulphide and/or
carbon dioxide, exit at the top part of the regeneration tower and after
having been cooled off, in a water or air exchanger. After the cooling water
is formed, and , is pumped into the regeneration tower to create reflux to
limit the losses of amine. Figures 13.2 and 13.3 show the process diagram
of the glycol-mine sweetening and of amine storage.
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Fig. 13.1 Glycol-Amine sweetening Unit

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Fig. 13.2 Glycol-Amine sweetening Unit

Process flow diagram
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Fig. 13.3 Amine storage process flow diagram

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13.2 DESCRIPTION AND FUNCTIONING OF:
13.2.1 Absorption Column

The absorption column is a piece of equipment capable of removing acid
gas. This occurs through the plates with allow an intimate contact between
the absorbent liquid and the gas that to be treated. This type of column
operates better at high pressure.
The quantity and nature of the acid compound present in natural gas
determines the quantity and composition of the absorbent in circulation.
Ethanolamines are most commonly used, mono-ethanolamine and di-
ethanolamine are more effective for the contemporary removal at H2S and
CO2 from natural gas. and triethanolamine which is highly selective towards
H2S.
Some mixtures of these amines can also be used, for instance formulated
amines.
Whatever the nature of the liquid absorbent, it is fed at the top of the
sweetening column, then flows down through a series of contacting plates.
The absorbent flows towards the bottom of the column absorbing the H2S
and/or CO2 present in the gas. The gas flows counter currently towards the
top and is forced to bubble in the liquid present in each plate where the
reaction and absorption of the acid gases to the amine occur.
For this type of absorption, several contact stages are necessary. Typically
there are around up-to 50 plates installed in an absorption column.
13.2.2 Gas Scrubber

Normally, a separator called gas scrubber is located upstream the
sweetening column and its task is to hold any possible absorbent carryover
that is in the gas.
To improve the separation effect, a DEMISTER or a liquid removal pack is
installed on the separator.
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13.2.3 Regeneration Column

The regeneration column has typically 30 contacting plates and operates at
low pressure. The acid solution enters near the top of the column and goes
counter current the acid stream generated in the re-boiler that goes up
towards the top of the column. This stream originates from the boiling that
occurs on the re-boiler and is mainly composed of water vapour (caused by
the water present in the solution) and acid gases (H2S and/or CO2).
In the tower the rich amine solution gets warm and releases the acid gases
that had absorbed becoming a lean solution (low H2S and/or CO2) that can
be reused to extract more acid gases. In the top of the column a reflux of
cold liquids, mainly condensed water, helps to condense the heavier
fractions (MEA-DEG) minimizing any solvent losses.
The regeneration of the solution is facilitated by low pressure and high
temperature, on the other hand the absorption is facilitated by high pressure
and low temperature.
In the regeneration column, the pressure is atmospheric or slightly superior,
whereas the temperature is linked to the type of absorbent.
In the case of glycol-amine (75% GDE, 20% MEA, 5% H20) the
regeneration temperature is of 155 °C whereas in the specific case of MEA
the temperature is of 105 ÷110 °C. This is due to the low boiling
temperature of MEA. Care should be taken no to heat the amine solutions
above their recommended maximum operating temperature to avoid
thermal degradation of the amine.
13.2.4 Re-boiler
The re-boiler is that piece of equipment capable of heating the amine
solution at the above-mentioned temperature values so that the water
present evaporates capturing H2S and/or CO2 present in the rich amine
solution.
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The acid gases and steam form in the re-boiler exit the re-boiler and go
back into the regeneration column to strip H2S and/or CO2 from the amine
solution which comes down from the top of the column.
The regenerated solution goes out of the re-boiler with low amounts of
carbon dioxide and hydrogen sulphide (lean solution) and is gathered at the
bottom of the regeneration column where it is pumped, filtered, cooled and
re-injected once again into the absorption column.
13.2.5 Reflux Drum

Acid gases, H2S and CO2 exit at the top of the regeneration tower and are
cooled in a water or air cooled exchanger, there the water present is
condensed and is collected in an appropriate separator. This water is re-
inserted, through a pump, in the re-generation column to create a reflux
capable of avoiding or at least limiting amine solution losses.
Acid gases H2S and/or CO2 are sent to flare or, if the quantity justifies this,
to a plant for the production of sulphur to meet environmental requirements.
13.2.6 Operation
The pressure and temperature parameters for a sweetening plant are
specific for each individual plant, but some common criteria remain.
As it has been stated, to have a good operation, it is necessary to operate
the absorber at a relatively low temperature, and that the pressure in the
adsorber column is as similar as possible to the design pressure.
The temperature has to be regulated so as the amine solution is always
hotter than 15÷20 °C to the gas temperature to avoid hydrocarbon
condensation and foaming in the absorber. This kind of temperature
regulation is carried out by operating gas inlet exchanger.
The concentration of the lean amine absorbent has to be as pure as
required by design after the regeneration, this is fundamental for the
absorption of hydrogen sulphide and/or carbon dioxide to the required
levels.
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To reach a good regeneration of the amine solution, low operating pressure

equal to or slightly above the atmospheric pressure and high temperature
have to be created in the regenerator column.
Amine regeneration occurs through heating and stripping in the

regeneration column. The temperature profile in the regeneration column is
set by the reboiler temperatture and it depends on the type of absorbent
solution used. For example, for an aqueous solution of MEA (80% H2O
20% MEA) the regeneration temperature has to be 105÷110 °C, but by
adding DEG to the solution a regeneration temperature of 145÷150 °C is
needed to remove the H2S that otherwise would remain in the amine
solution.
In the regeneration column it is important not only to control the bottom

column temperature (regeneration temperature) but also the overhead
temperature, because the higher this temperature, the greater the losses of
amine solution due to evaporation. This temperature cannot be different
from the boiling temperature of water, so the head temperature must be
around 95-100 °C.
The heating of the amine solution can cause the decomposition of the
amines, and also some impurities will react with the amines producing the
formation of salts. These salts can be corrosive and reduce the absorbing
power of the amine solution, therefore a process is needed to eliminate
these salts, and generally a small distillation unit is installed to remove
these salts.
To avoid any further decomposition vacuum distillation is employed to avoid
overheating the amine solution. In this type of plant the vacuum level is
fundamental and it must always stay at about –680 mm H2O. The
temperature depends on the concentration of water and the type of amine
used.
To eliminate a greater quantity of H2S from the amine solution, STRIPPING
GAS can be used in the regeneration column, but this is not recommended
when the sour gas is sent to a sulphur recovery unit. By using sweet gas
counter current to the rich amine solution, part of the acid gas present in the
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solution is eliminated and the concentration of the solution is improved at a

lower operating temperature.
During plant operation iron sulphide may form due to a chemical reaction
between the acid gases and the metal of the vessels and piping of the unit.
This can be prevented by using non-corrosive amines or amines with
corrosion inhibitors. If iron sulphide is formed its removal is very important
because it will cause foaming and eventually plug some of the exchangers.
To control this impurity, appropriate filters must be installed and during
maintenance must be carefully serviced since iron sulphide is highly
inflammable and when it burns it develops high concentrations of H2S and
SO2, both very dangerous for the personnel. As a consequence filter
maintenance has to be carried out with appropriate flame retardant
equipment and personnel must wear masks for protection.
Different types of sweetening plants (Figs. 13.4, 13.5, 13.6, 13.7) are shown
in the following pages, each of these plants uses different amine solutions,
but the functioning principles are substantially the same.
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Fig.13.4 – Sweetening plant

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Fig. 13.5 Sweetening plant

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Figure 13.6 Sweetening plant.

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Figure 13.7 Sweetening plant.

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14. SULPHUR RECOVERY PLANT
14.1 SCHEME AND FUNCTIONING CLAUS PROCESS

The process uses the acid gas rich stream from the sweetening process as
feed to produce liquid or solid sulphur. The process is widely known as the
"Claus" process. Developed about 1890 it is applicable for production of
sulphur from acid gas streams containing about 20% to 100 H2S.
The original Claus process comprised oxidation of hydrogen sulphide with
air over bauxite or iron or catalyst in a single reactor. According to Gamson
and Elkins the first significant advance was made in 1937 by I. G. Farben-
industrie. Instead of burning the H2S directly over the catalyst, they burned
1
/3 of the H2S to sulphur dioxide in a waste heat boiler. The sulphur dioxide
was then reacted with the remaining H2S over bauxite at 700-750° F. The
primary advantage of this arrangement is that the total heat of reaction
evolved in the catalytic converter is greatly reduced thus allowing for better
temperature control. Another development attributed to I. G. Farben-
industrie was the high temperature (up to 1,000° C) non-catalytic
combustion of H2S with air, to produce sulphur directly. This non-catalytic
conversion of H2S to sulphur produces yields that are asserted to range as
high as 90%.
Chemistry of Claus Process
The process chemistry can be summarized in the following reactions:
Thermal 3 H2S + 3/2 O2 = SO2 + 2 H2S
Catalytic SO2 + 2H2S = 3/n Sn + H2O
Overall 3 H2S + 3/2 O2 = 3/n Sn + H2O
Sulphur exists in several forms (S4,S6,S8), so the modern practice is to use
Sn. In the Claus process Only a certain amount of air is admitted to the
furnace to allow enough SO2 to be produced so that the ratio of H2S and
SO2 for conversion to sulphur is 2:1. This is a non-reversible combustion of
H2S that produces large quantities of heat. The catalytic reaction takes place
over a bauxite catalyst at a fairly low temperature (but high enough to keep
the sulphur liquid).
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In chemical equilibrium reactions there are several factors that may

influence their completeness and the resulting production of sulphur. They
are as follows:
- Concentration of H2S and SO2
- Temperature of the reaction
- Pressure of the reaction
The concentration of H2S and SO2 are important because the catalyst works
within certain limits. If the concentrations drop below 2%, the molecules
become too distant to allow the reaction to occur within the time the gases
remain in the converter. Similarly, concentrations over 25% would result in
excess heat, water, and sulphur forming which may overload the catalyst.
Alternate Flow Process
The recovery of sulphur from hydrogen sulphide has led to the development
of several processing methods, all of which are based on the Claus reaction
principles. The following two basic variations of the Claus sulphur process
account for the design of most of the commercial Claus plants:
1. Straight-through process (over 50% H2S in feed gas)
2. Split-flow process (lower than 50% H2S in feed gas)
The process selected for a particular plant will depend, as a general rule, on
the H2S concentration in the acid gas and the volume of gas handled
The primary difference between the different processes is the way in which
heat balance is maintained in the process. Fig. 14.1 shows a "once through"
Claus unit process flow scheme using hot gas by-pass for reheat. The acid
gas feed is combined with stoichiometric air to burn 1/3 of the total H2S to
SO2 and all hydrocarbons to CO2. Combustion of the H2S takes place in the
burner and reaction chamber. The high temperature combustion mass flows
to the waste heat boiler where heat is removed from the combustion gases.
A part of the hot gas from the waste heat boiler is by passed in order to
reheat the gas from the sulphur condenser to reaction temperature before it
is introduced to the catalyst beds in the converters or reactors. Condensed
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sulphur is withdrawn from the first sulphur condenser. The cool gas leaving
the first sulphur condenser is combined with the first hot gas by-pass
stream and fed to the first reactor.
Sulphur must be removed from the condenser at a temperature in the 320°
F. range. Because of a composition change which occurs at about 320° F,.
the viscosity of liquid sulphur increases very rapidly above that temperature.
Consequently, the temperature of the sulphur must be kept below 320° F. or
the sulphur will be so thick and viscous that it is very difficult to remove from
the condenser. Preferred temperature for inlet to the catalytic converters or
reactors is in the 450° F range. However, it must be above the sulphur dew
point to avoid condensation of liquid sulphur on the catalyst bed. Any
condensation will cause plugging and catalyst deactivation. This explains
the necessity for the hot gas bypass to maintain a satisfactorily high
temperature level at the reactor inlets.
The mixture of hot gas and cooled stream flows downward through the first
catalytic converter and then into the condenser where the temperature is
once more lowered to the 300° F. range and liquid sulphur removed. Cooled
gases are then combined with the second hot gas bypass flow to balance
temperature at the inlet of the second reactor, further conversion of H2S and
SO2 to sulphur is accomplished in the second reactor bed and the gases
are cooled again for sulphur removal.
Use of the once through process is highly desirable from a sulphur recovery
standpoint. If the once through process can be used, approximately 2/3 of
the total sulphur production will come from the condenser immediately
following the waste heat boiler. Goar has shown a sketch of a typical waste
heat boiler in a once through process. The sketch by Goar is shown in Fig.
14.2. Typically the gases leave the combustion chamber at about 2300° F in
their first pass through the waste heat boiler. On the second pass they are
cooled to the range of 550° F before flowing to the first sulphur condenser.
The hot gas bypasses are withdrawn from the furnace at approximately
1100° F.
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Fig. 14.3 shows a modification of the once-through process which is used

when the acid gases entering the plant are low in H2S, below approximately
25%. In these cases there is not sufficient heat of reaction to raise the entire
acid gas stream to satisfactory temperature levels.
Fig. 14.1 Claus “once through” process flow
Fig. 14.2 Typical reaction furnace and waste heat

boiler
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Consequently, only the portion of the gases to be burned is mixed with air
and introduced to the burner. They flow through the waste heat boiler as
before, with a portion of the gases being combined with the un-combusted
2
/3 of the acid gas before being introduced into the first reactor. A hot gas
bypass is utilized for temperature control at the inlet of the second reactor.
As in the once-through process, the split stream process utilizes
stoichiometric air to burn 1/3 of the H2S to S02 and all of the hydrocarbons to
CO2.
Sulphur recovery varies for different process configurations, and for the
number of catalytic stages used. Typical sulphur recovery for different
process are given below.
• Number of catalytic stages
2 stages 95-96%
3 stages 96-97%
• Tail gas treatment 99.8%
There is a practical limit to the number of catalytic stages that can be

installed to improve total sulphur recovery, and for that reason above 97%
sulphur recovery, another type unit has to be installed to treat the Claus tail
gases, the tail gas treating unit.
Fig. 14.3 Claus “split stream”

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15 TAIL GAS TREATMENT
15.1 GENERAL
As shown in Fig. 15.1, the Tail gas treating is a process subdivided in three
basic steps: heating and reducing all sulphur compounds to H2S; cooling
and quenching; and H2S absorption, stripping and recycle.
The tail gas from the Claus unit is heated and reacted with a reducing gas,
commonly hydrogen or a mixture of hydrogen and carbon monoxide, over a
catalyst bed cobalt-molybdate or alumina bauxite to reduce the sulphur and
sulphur dioxide. The hydrogen rich gas is obtained by auto-thermal
reforming of natural gas with air.
The gas from the reactor is cooled next in a downstream heat exchanger
and a cooling tower to remove all the heat from the gas. Quenching of the
gas takes place at about atmospheric temperature. Water vapour in the
process gas is condensed and condensate is sent to a sour water stripper.
After the gas is cooled the gas is treated with a selective amine or
triethnolamine to remove the H2S from the gas stream with absorption of
little or no CO2. The H2S is then stripped from the absorbing solution and
recycled to the feed inlet to the Claus sulphur unit.
Since the catalytic hydrogenation is carried out at temperatures in the range
of 570.°F the gas must be cooled before they are contacted with the
alkanolamme solution. The treated gas from the top of the absorption
column contains small enough quantities of H2S that can be burned in the
standard Claus incinerator. (Fig. 15.1)
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Fig. 15.1 Tail gas treating plant

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Eni Corporate University

JUNIOR PRODUCTION ENGINEER

Lecturer: Eng. Romano Bianco

Code: IMG017-E-A0 Rev.: 02 Date : 30/07/2004 Pages number: 94

1 NATURAL GAS BOOKLET N° 1

2 NATURAL GAS PROCESSING BOOKLET N° 1

3 SURFACE WELL EQUIPMENTS BOOKLET N° 1

4 COLLECTION AND TREATMENT CENTRE BOOKLET N° 1

5 TREATMENT LINE BOOKLET N° 2

6 GLYCOL DEHYDRATION SYSTEM BOOKLET N° 2

7 COOLING TREATMENT PLANTS BOOKLET N° 2

8 SOLID BED NATURAL GASOLINE PLANT BOOKLET N° 2

9 LPG PLANT BOOKLET N° 2

10 PROPANE DEHYDRATION BOOKLET N° 2

11 COS TREATING BOOKLET N° 2

12 MERCAPTAN TREATING BOOKLET N° 2

14 SULPHUR RECOVERY PLANT BOOKLET N° 2

15 TAIL GAS TREATMENT BOOKLET N° 2

16 COMPRESSION UNITS BOOKLET N° 3

17 DEHYDRATION BY SOLID BEDS BOOKLET N° 3

18 SOUR WATER STRIPPER PLANT BOOKLET N° 3

19 FLARE SYSTEM BOOKLET N° 3

20 NITROGEN PRODUCTION BOOKLET N° 3

21 COMPRESSED AND INSTRUMENT AIR

22 FUEL GAS SYSTEM BOOKLET N° 3

23 WATER TREATMENT SYSTEM BOOKLET N° 3

24 FIRE FIGHTING SYSTEM BOOKLET N° 3

25 POWER SUPPLY SYSTEM BOOKLET N° 3

26 ALARM AND SHUT-DOWN SYSTEMS IN GAS PLANT

6 GLYCOL DEHYDRATION SYSTEM 7

6.2 SCHEME AND FUNCTIONING 7

6.3 STRUCTURE AND FUNCTIONING OF: 12

7. COOLING TREATMENT PLANTS 28

7.2 LIQUID HYDROCARBON RECOVERY BY MEANS OF COOLING 36

7.3 SCHEME AND FUNCTIONING 38

8. SOLID BED NATURAL GASOLINE PLANT 49

8.2 SCHEME AND FUNCTIONING 49

8.3 STRUCTURE AND FUNCTIONING OF: 53

9.1 SCHEME AND FUNCTIONING 57

13.1 SCHEME AND FUNCTIONING 74

13.2 DESCRIPTION AND FUNCTIONING OF: 79

14. SULPHUR RECOVERY PLANT 88

14.1 SCHEME AND FUNCTIONING CLAUS PROCESS 88

15 TAIL GAS TREATMENT 93

6 GLYCOL DEHYDRATION SYSTEM

6.2 SCHEME AND FUNCTIONING

The level of glycol in the tower bottom, is maintained by a level controller

Fig. 6.2 - Gas Dehydration Unit - Closed circuit alternative

6.3 STRUCTURE AND FUNCTIONING OF:

6.3.1 Dehydration column

Figure 6.4 – Dehydration column with bubble cap trays

Bubbling cap or valve trays

Figure 6.5 – Bubble cap Tray

6.3.2 Circulation pumps

Fig. 6.6a Reciprocating pump

Fig. 6.6b Reciprocating Pump dimensions and performance data

Fig.6.7 - Reciprocating pump

Fig. 6.8 Typical reciprocating pump unit

6.3.3 Calculation of the glycol flow

Water content = 300x1.000.000/1000= 300.000 g/d = 300 Kg/d of water.

Water content, at required gas flow rate, is 0 50x1.000.000/1.000= 50.000

Experimental data shows that, in order to eliminate 1 Kg of water, 25 Kg of

Figure 6.10 – Regenerator (typical arrangement for a small unit)

A more common arrangement for a high capacity dehydration unit, usually