Treatment of Oil

More than 80% of the crude produced in the world contains various amounts
of water. The treating of oil, therefore, consists of dehydration (i.e. removal of
water) and desalting, if required, by methods such as using a settling tank,
heater treaters, or electrical dehydrators and desalters such as water wash or
water dilution. The objective is to remove water and salt contaminants from
the oil to meet the processing requirements in the refinery. The crude oil supplied
to the refinery should have water content less than 1% and salinity less
than 50 mg per litre (50 ppm).
Dehydration – This treatment is principally the treatment of emulsion. The
emulsion is defined as a mixture of two mutually immiscible liquids, one of
which is dispersed as droplets in the other and is stabilised by an emulsifying
agent’s film envelope around the droplet. The dispersed phase is known
as the internal phase and the liquid surrounding the dispersed droplets is
the external or continuous phase. Water-in-oil emulsion, that is, water as
dispersed phase and oil as continuous phase, is most common. Emulsifying
agents, such as formation fines, silts, asphaltenes, waxes and resins stabilise
the dispersion.
Methods employed in dehydrating crude petroleum emulsions may
be classified into six groups, such as: (1) gravity settling method, (2) heat-
treatment
method, (3) electrical methods, (4) chemical-treatment method,
(5) centrifugal method and (6) filtration method. Of these six different methods
of treatment, the first four have found extensive application in the petroleum
industry; the fifth is less used than the first four methods; and the sixth
method is employed chiefly in experimental tests.
Gravity settling method – If crude petroleum contains water in suspension,
some, or perhaps all, will often settle out on prolonged standing, by reason
of the greater density of water. This separation will usually be slow and
incomplete and, in the case of thoroughly emulsified water, will perhaps
merely take the form of downward concentration of the suspended water
droplets, without actual coalescence, still permitting some water-free oil to be
skimmed off the top of the fluid. The lower portion of the fluid will, of

course, contain a higher percentage of water than before gravitational settling

occurred.

Gravity settling is often combined with other processes of treatment to

accomplish final and complete separation of the two fluids, after the emulsion

has been ‘broken’ by appropriate means. For example, certain chemical

methods of treatment are effective in bringing about emulsification, but

treatment by this method is followed by a period of gravity settling, during

which the water is liberated and is permitted to settle out, leaving the supernatant

oil practically free of water.

Heat-treatment methods – Application of heat to petroleum emulsions is

often an effective means of accomplishing their dehydration and is, in many

instances, used to assist other processes. Heat aids in bringing about separation

of water from petroleum emulsions in three ways: (1) by reducing the

viscosity of the oil, so that gravity may more readily operate in settling out

the heavier water; (2) by effecting change in the interfacial tension relationships

and colloidal properties of the emulsifying agent; and (3) if the temperature

is carried high enough, by actually bringing about a change from the

liquid to the gaseous state, the steam formed bursting the enclosing oil films

about the water droplets. The equipment used for such treatment is known
as heater treater. The most commonly used single well lease treater is the

vertical treater as shown in Figure 6.5.

Vertical heater–treater.

Flow enters the top of the treater into a gas separation section. This section has an
inlet diverter and a mist extractor.

The liquids flow through a downcomer to the base of the treater, which

serves as a free-water knockout section. If the treater is located downstream of a

free-water knockout, the bottom section can be very small. If the total

wellstream is to be treated, this section should be sized for 3 to 5 min retention

time for both the oil and the water to allow the free water to settle out.

This will minimise the amount of fuel gas needed to heat the liquid stream

rising through the heating section. The end of the downcomer should be

slightly below the oil-water interface to ‘water wash’ the oil being treated.

This will assist in the coalescence of water droplets in the oil.

The oil and emulsion rise over the heater fire-tubes to a coalescing section

where sufficient retention time is provided to allow the small water particles

in the oil continuous phase to coalesce and settle to the bottom.

Treated oil flows out of the oil outlet. Any gas, flashed from the oil due to

heating, flows through the equalising line to the gas space above. Oil level is

maintained by pneumatic or lever operated dump valves. Oil-water interface

is controlled by an interface controller, or an adjustable external water leg.

For most multi-well situations horizontal treaters are normally required.

The working principle of these treaters remains the same.

Electrical method – When brought within the field of influence of a highpotential

alternating current, the dispersed water droplets of a petroleum

emulsion coalesce to form larger water aggregates, which readily settle out

under the influence of gravity. In this process, the emulsion is generally heated

moderately to reduce viscosity and facilitate settling. Very complete separation

of the water and oil is quickly effected at small cost by this method.

Theory indicates that the droplets of emulsified water, when passing

between two electrodes upon which a high potential is imposed, become

charged by induction. One side of each globule is negatively charged, the

other positively and attraction between opposite charges causes the water

droplets to align themselves, forming a chain between the electrodes. When

this occurs, a discharge of electricity passes through the chain from one electrode
to the other. As a result, the water globules comprising the electrical

path coalesce and form one large drop of water, which readily settles from

the oil under the influence of gravity.

Dehydration by the electrical method occurs in two steps. In the first step,

the minute water globules coalesce, forming larger masses; and in the second,

the larger masses settle from the oil under the influence of gravity.

Figure 6.6 illustrates a typical design of a horizontal electrostatic treater.

Horizontal electrostatic treater

Here an AC and/or DC electrostatic field is used to promote coalescence of

the water droplets. It is experienced that such electrostatic treaters are efficient

at reducing water content in the crude below the 0.5–1.0% basic sediment

and water (BS & W) level. This makes them particularly attractive for
desalting applications.

Chemical method – Chemicals used to break the emulsion known as demulsifiers

are sold under various trade names, such as Tretolite, Visco and Braksit.

Demulsifiers act to neutralise the effect of emulsifying agents. Typically, they

are surface active agents and thus their excessive use can decrease the surface

tension of water droplets and actually create more stable emulsions.

There are four important actions required of a demulsifier: (1) Strong

attraction to the oil-water interface, (2) flocculation, (3) coalescence and

(4) solid wetting.

When these actions are present, they promote the separation of oil and

water. The demulsifier must have the ability to migrate rapidly through the

oil phase to the droplet interface, where it must compete with the more
concentrated

emulsifying agent. The demulsifier must neutralise the emulsifier

and promote a rupture of the droplet interface film which causes coalescence.

With the emulsion in a flocculated condition, the film rupture results

in rapid growth of water-drop size.

The way the demulsifier neutralises the emulsifier depends upon the type

of emulsifiers. It would be unusual if one chemical structure could produce

all four desirable actions. A blend of compounds is therefore used to achieve

the right balance of activity.

The demulsifier selection should be made with the process system in

mind. If the treating process is a settling tank, a relatively slow acting compound

can be applied with good results. On the other hand, if the system is

a chemelectric process where some of the flocculation and coalescing action

is accomplished by an electric field, there is a need for a quick-acting compound,

but not one that must complete the droplet-building action.

Centrifugal method – Centrifugal force, developed mechanically by rapid

rotation of an oil-water mixture, is effective in bringing about separation of

the two fluids. The effect is identical with that of gravity but is many times as

powerful. Centrifuges capable of developing rotational speeds of 15,000 rpm

develop a force equivalent to 13,000 times that of gravity. Efficiency in separation

of the oil and water is dependent directly upon their relative

densities

– the greater the difference in specific gravities, the more effective

the separation will be.

A centrifuge capable of bringing about complete separation of the two fluids

from an emulsion must have a high speed of rotation. Machines thus

far developed for large-scale continuous operation consist of a metal bowl

mounted on the upper end of a vertical shaft that is rapidly rotated by a

direct-connected electric motor. Belt-driven machines may also be secured if

desired. The oil-water mixture, usually preheated to reduce viscosity, is fed

into the bowl at its centre through a pipe that discharges into the bowl near

the bottom. The selective action of centrifugal force then causes the water
(the denser of the two fluids) to move outward toward the perimeter as it

moves upward toward outlets in the cover of the bowl. A clear-cut cylindrical

plane of separation is developed between the two fluids, the position of

which depends upon the percentages of oil and water present. Clean oil overflows

through an outlet in the top of the bowl near the centre, while water

escapes through a second outlet near the outer perimeter of the bowl. Sand

and other suspended impurities tend to follow the water, though the coarser

solids generally remain in the bowl and must occasionally be removed by

hand methods after stopping rotation and removing the cover.

Filtration method – In this method, processes are designed to separate emulsified

oil and water by filtration under pressure through various porous

mediums. Such filtering medium can be water-wet or oil-wet.

Water passes through such a water-wet filtering medium, and if the pore

spaces of the filter are sufficiently small, the oil phase will be left on the

upstream side of the filter. Conversely, an oil-wet filter cloth will pass oil but

not water. Excelsior, sand, diatomaceous earth, glass wool and other filtering

mediums have also been used with more or less success, often with the aid

of the familiar filter press, so widely used in wax filtration in oil refining

and for like purposes in other industries. In addition to their filtrative properties,

the sharp angular edges and projections that such materials present

are to some extent successful in altering the interfacial tension relationships

between the water and the oil. ‘Hay tank’ is one such treater employing the

filtrative principle.

Desalting – The water content of crude oil can be brought to the acceptable

limit of less than 1% by electrostatic treatment; however, the salinity of the

oil might be still higher than the accepted limit fixed by refinery.

Desalting operation is carried out mainly to reduce the salinity of crude

oil. Desalting, which follows the initial dehydration, consists of

1. Adding dilution (or fresh) water to the crude.

2. Mixing this dilution water with the crude to dilute saline water.

3. Emulsion treating or second stage dehydration to separate the crude

and brine phase.

A schematic of 2-stage desalting is shown in Figure 6.7. In 2-stage desalting,

the required water injection rate is usually 5–7% of the crude flow rate.

The mixing tee mixes fresh dilution water and shears dilution water into

droplets and disperses it throughout the crude.

Desalting in two stages.

 Treatment of Gas

The major treatments made to the produced gases are dehydration and

sweetening.

Dehydration – The major reasons for dehydrating natural gas are

1. Natural gas can combine with liquid or free water to form hydrate

that can plug valves, fittings, or even pipelines.

2. When liquid water is present, natural gas becomes corrosive, especially

if CO2 and/or H2S are also present.

3. Water vapour in natural gas can condense in the pipeline causing

slug flow.

4. Water vapour increases the volume and decreases the heating value.

There are two methods of dehydration based on the principle of either

absorption or ‘adsorption,’ and these are

1. Glycol dehydration

2. Solid bed dehydration

The ‘glycol dehydration process’ is an absorption process, where the water

vapour in the gas stream becomes dissolved in a relatively pure glycol liquid

solvent stream. Glycol dehydration is relatively inexpensive, as the water can

be easily ‘boiled’ out of the glycol by the addition of heat. This step is called

‘regeneration’ or ‘reconcentration’ and enables the glycol to be recovered for use

in absorbing additional water with minimal loss of glycol. The type of glycol

commonly used is either di-ethylene glycol (DEG) or tri-ethylene glycol (TEG).

Figure 6.8 shows a flow diagram for TEG dehydration plant.

TEG dehydration unit – flow diagram.

Here the wet natural gas first flows through an inlet separator or scrubber to
remove all

liquid and solid impurities. Then the gas flows upward through the absorber

or contactor where it is contacted countercurrently and dried by the glycol.

Finally, the dried gas passes through a gas-glycol heat exchanger and then

into the sales line. Concentrated or ‘lean’ glycol enters the top of the contactor
and flows downward and absorbs water from the rising natural gas.

The water-rich or ‘wet’ glycol leaves the absorber and flows through a

larger coil in the accumulator or surge tank where it is preheated by the

hot lean glycol. After this glycol–glycol heat exchange, the rich glycol enters

the stripping column and flows down the packed bed section and into the

reboiler. Steam generated in the reboiler strips water from the liquid glycol

as it rises up the packed bed and is finally vented from the top of the stripper.

The hot reconcentrated glycol flows out of the reboiler into the surge tank

where it is cooled. Finally, the ‘lean’ glycol is pumped through the glycol–gas

exchanger and is fed back into the top of the absorber.

‘Solid bed dehydration’ systems work on the principle of adsorption.

Adsorption involves a form of adhesion between the surface of the solid

desiccant and the water vapor in the gas. The water forms an extremely

thin film that is held to the desiccant surface by forces of attraction, but

there is no chemical reaction. The desiccant is a solid, granulated drying or

dehydrating medium with an extremely large effective surface area per unit

weight because of a multitude of microscopic pores and capillary openings.

A typical desiccant might have as much as 4 million square feet of surface

area per pound.

Figure 6.9 shows a flow diagram for a typical two-tower solid desiccant

dehydration unit.
 Solid bed dehydrator – flow diagram

The essential components of any solid desiccant dehydration

system are

1. Inlet gas separator.

2. Two or more adsorption towers (contactors) filled with a solid

desiccant.

3. A high-temperature heater to provide hot regeneration gas to reactivate

the desiccant in the towers.

4. A regeneration gas cooler to condense water from the hot regeneration

gas.

5. A regeneration gas separator to remove the condensed water from

the regeneration gas.

6. Piping, manifolds, switching valves and controls to direct and control

the flow of gases according to the process requirements.

In the drying cycle, the wet inlet gas first passes through an inlet separator

where free liquids, entrained mist and solid particles are removed.

In the adsorption cycle, the wet inlet gas flows downward through the

tower. The adsorbable components are adsorbed at rates dependent on their

chemical nature, the size of their molecules and the size of the pores. The

water molecules are adsorbed first in the top layers of the desiccant bed.

Dry hydrocarbon gases are adsorbed throughout the bed. As the upper layers

of desiccant become saturated with water, the water in the wet gas stream

begins displacing the previously adsorbed hydrocarbons in the lower desiccant

layers. Liquid hydrocarbons will also be absorbed and will fill pore

spaces that would otherwise be available for water molecules.

At any given time, at least one of the towers will be adsorbing while the

other towers will be in the process of being heated or cooled to regenerate

the desiccant. When a tower is switched to the regeneration cycle, some wet

gas (i.e. the inlet gas downstream of the inlet gas separator) is heated to

temperatures of 450–600°F in the high-temperature heater and routed to the

tower to remove the previously adsorbed water. As the temperature within

the tower is increased, the water captured within the pores of the desiccant

turns to steam and is absorbed by the natural gas. This gas leaves the top

of the tower and is cooled by the regeneration gas cooler. When the gas is

cooled, the saturation level of water vapor is lowered significantly and water

is condensed. The water is separated in the regeneration gas separator and

the cool, saturated regeneration gas is recycled to be dehydrated. This can be

done by operating the dehydration tower at a lower pressure than the tower

being regenerated or by recompressing the regeneration gas.

Sweetening – Gas sweetening is processing of natural gas to remove acid

gases such as hydrogen sulphide and/or carbon dioxide which form corrosive

acids in the presence of moisture and ultimately lead to corrosion of metals.

Hydrogen sulphide and carbon dioxide gases are found as a constituent of natural

gas in many fields. The concentration of these gases may range up to 10%.

Removal of hydrogen sulphide to a very low concentration, typically 1/4 grain

per 100 scf (8 ppmw, 4 ppmv) is desired for pipeline specifications and for all

other purposes. Removal of CO2 to reasonably low levels (up to 2.5 mole%) is

generally required for all practical purposes. The removal of H2S from natural

gas is usually accompanied by the removal of CO2. The removal of CO2 is also

desirable if the gas contains moisture or if it has a low heating value.

There are many processes for gas sweetening as mentioned below:

1. Amine process – This is generally used for large capacity plants and

where gas streams contain more than 0.075% of acid gas. The type of

amines commonly used are

a. Di-ethanol-amine (DEA) – By using this amine, the H2S and CO2

as well as mercaptans can be removed. This process is useful for

natural gas as well as refinery gas applications.

b. Methyldiethanolamine (MDEA) – This amine process is suitable

for selective removal of H2S to pipeline specifications.

2. Physical solvent process – This process is suitable where bulk removal

and selective removal of acid gas is desired, heavy hydrocarbon

quantity (% age) in feed gas is low, and partial pressure of acid gas

in feed is greater than 50 psig.

3. Hot carbonate process – This process can remove CO2 to very low
specifications

and H2S to pipeline specifications.

4. Batch process – For example,

Iron sponge process

LO-CAT

Chemsweet

Molecular sieve

MDEA Process – Figure 6.10 shows a layout of an MDEA sweetening plant.

 MDEA sweetening unit – flow diagram.

Here the sour gas first passes through a knock-out drum where liquid carryover

is separated. Liquid collected at the bottom of the drum is pumped out

to the condensate treating section. Upon leaving the knock-out drum, the

gas enters the amine absorber (tray type) where it comes into countercurrent

contact with the aqueous solution of MDEA.

The absorber column normally contains 12 to 18 valve trays. The lean

MDEA solution enters the column from the upper section at 45°C and

gas enters at the bottom of the column. Different liquid feed nozzles on
the column give the flexibility of allowing the correct feed plate to be

selected to obtain the required results. The treated gas leaves the top of

the absorber containing less than 4 ppm (vol) H2S at a temperature of

40–44°C.

The treated gas enters a knock-out (KO) drum in which the liquid phase

(condensed water, amine carry-out) is separated from the gas stream.

The liquid from KO drum is sent to rich amine flash drum. The treated

gas leaves from the top of the KO drum and is piped to triethyleneglycol
drying/dehydration unit. The rich amine solution flows from the bottom of

the absorber to the rich amine flash drum and then to the rich/lean amine

exchanger. MDEA solution stripping is accomplished in the regenerator.

Stripping vapor (primarily steam) is generated in the reboiler. The acid

gases and the steam leave the top of the stripper and pass through a condenser,

where a major portion of the steam is condensed and cooled.

The acid gases are separated in a separator and sent to flare or to processing.

The condensed steam is returned to the top of the stripper as reflux.