PETROLEUM CRUDE PREPARATION

CRUDE PREPARATION
• Removal of water
• Removal of salt
• Separation of dissolved gases
There are main two impurities, water & salt which have multiple effects on processing of
crudes.
• PETROLEUM PREPARATION INCLUDES
• -drying (removal of water or dewatering)
• -desalting of petroleum,
• -and complete or partial removal of dissolved gas.
The light fractions of petroleum (gases from methane to butane) are valuable raw
materials for the chemical industry from which products such as solvents, liquid motor
fuel, alcohol, synthetic rubber, fertilizers, artificial fibre and other products of organic
synthesis are made. Therefore, it is necessary to reduce the loss of light fractions during
petroleum processing. Thus, all hydrocarbons derivable from petroleum need to be
preserved for subsequent processing.
Water Impurity

• About two-thirds of all petroleum is extracted in high humidity conditions.

Water layers can differ considerably by their chemical and bacteriological
contents.
• During the extraction of this mixture of petroleum with water layer, an
emulsion is formed.
• The water present in petroleum results in an increase in the transportation
price because of an increase in both volume and viscosity of the resulting
liquid to be transported.
• The presence of corrosive mineral salts in solution in the water leads to fast
deterioration of petroleum pumps and oil refining equipment.
• The presence of up to 0.1% of water in petroleum leads to intensive foam
formation in the rectification tower of oil refineries. Besides, it also affects
the condensation equipment.
Salt Impurity
• In the past, the technological processing scheme of older oil refineries could be used to
process crude petroleum with mineral salts contents of 100—500 mg/L. Petroleum with
a lower salt content is required in modern refineries. Thus, before oil processing, it is
necessary to completely remove salt from the petroleum by desalting.
• The presence of different types of salt impurities in petroleum affects pipe- lines and oil
pumps.
• The solids form scales in coolers/refrigerators and furnaces. This leads to a reduction in
the heat transfer coefficient of the scaled surface.
• The presence of mineral salts in the form of crystals in petroleum and in solution in
water leads to extensive corrosion of metallic parts of equipment and pipelines.
• Under favourable conditions, a part of magnesium chloride (MgCl2) and calcium chloride
(CaCl2) present in the water layer can be hydrolysed with the formation of hydrochloric
acid leading to corrosion of metal parts. Also, hydrogen sulphide is formed during
petroleum processing as a result of decomposition of sulphur compounds. This increases
the intensity of corrosion of metals in the presence of water. Hydrogen chloride in water
solution also corrodes metal parts.
• The requirement for petroleum quality before processing is very stringent: the contents
of salts should not be more than 40 mg/L in the presence of water, whose content
should only be up to 0.1%.
• These salts can be found in two forms: dissolved in emulsified water droplets in
the crude oil, as a water-in-oil emulsion, or crystallized and suspended solids.
• The negative effect of these salts in downstream processes can be summarized as
follows: salt deposit formation as scales where water-to-steam phase change
takes place and corrosion by hydrochloric acid formation. Hydrochloric acid is
formed by magnesium and calcium chlorides’ decomposition at high
temperatures (about 350 °C) as follows;
• CaCl2 + 2H2O → Ca(OH)2 + 2HCl
• MgCl2 + 2H2O → Mg(OH)2 + 2HCl
Electrostatic separators

The stronger AC/ DC field between the electrodes causes rapid movement of the remaining small
water droplets through electrophoretic attraction, causing the water droplets to collide, coalesce,
grow, and settle by gravity.
The process starts by mixing the raw crude oil with an appropriate amount of washing water also
known as dilution water. The washing water as a volume percent of the crude oil processed could be
between 3 to 10%, depending on the gravity of the crude oil – the heavier the crude oil, the more
the water required. Demulsifiers are added to the crude oil in this process step.
In order to promote the effective mixing between the organic and aqueous phases, and ensure the
proper dilution of the salts and minerals in the aqueous phase, a mixing valve is used which causes
a pressure drop and, as a result, a shear stress over the droplets that promotes an intimate water
and oil mixture. In addition to the mixing valve, upstream premixing device could be used, such as
spray nozzles at the point of water injection or static mixers, between the water injection point and
the mixing valve. High delta pressure in the mixing valve promotes smaller droplets, improves the
contact among the phases; however, very small droplets could yield a more stable emulsion, which
could cause problems in the separating vessel. Therefore, it is very important to balance both
effects in the selection of the operation pressure drop.
Then this mixture goes to the desalter, a horizontal cylindrical tank that
provides long enough residence time to separate the water and oil
mixture in two phases. Some water droplets diameters are so small
that they could not be separated by gravity; so, an electrostatic field
between two electrodes installed into the desalter is used to promote
coalescence. Due to the dipolar nature of the water molecule, this
electric field promotes an attraction with the other water molecules in
the neighbour droplets promoting coalescence. Either AC or DC fields
may be used and potentials from 12, 000 to 35, 000 volts.
One Stage

Two stages
Electrostatic separators
Formation of Petroleum Emulsions and Their Basic Properties
• In order to select the proper drying process, it is necessary to know both the mechanism of
formation and properties of petroleum emulsions.
• Usually, no emulsions are formed within the petroleum layer. Emulsion formation begins during
the movement of petroleum to the mouth of the oil well and intensifies during further transport
of petroleum in pipes (i.e. emulsions are predominant where there is the potential for continuous
mixing of petroleum and water). The intensity of emulsion formation in an oil well depends on
the method of petroleum extraction. This, in turn, is defined by the character of the oil wells, time
of its operation and physical-chemical properties of the petroleum.
• When petroleum is extracted from oil wells using the natural layer pressure (which is typical in
the initial period of oil well operation), there is usually a very high rate of extraction of the oil
from the oil well. The intensity of petroleum mixing with water in elevating pipes of the oil well
increases due to dispersion of the dissolved gases at decreasing pressure. This leads to emulsion
formation at the early stages of movement of the petroleum-water mixture.
• During deep pumping extraction of petroleum, emulsion formation occurs in the valves, in the
pump cylinders and in the elevating pipes during the reciprocating movement of pump bars. Air
sometimes mixes with the gas in an oil well and oxidizes a part of the heavy hydrocarbons to form
asphaltenes- resinous materials. Thus, the presence of salts of organic acids as well as
asphaltenes-resinous materials leads to emulsion formation. This type of emulsion has a very high
stability.
Emulsion problem in processing of the crude
• It is important to distinguish two phases in emulsions - the discontinuous and
continuous phases. The continuous phase is the liquid in which very small
droplets of another liquid are dispersed. The discontinuous phase is the liquid
that is dispersed in the form of fine droplets in the continuous phase.
• Two types of emulsions are distinguishable - "oil in water" and "water in oil". The
type of emulsion formed basically depends on the volume ratio of the two
phases. The continuous phase is the liquid with the greater volume. In practice
the most frequently known emulsion is the water in oil emulsion.
• Emulsifiers that are soluble in water (hydrophilic) promote the creation of oil in
water emulsion. Alkaline soaps, starch and so on are such hydrophilic emulsifiers.
Hydrophobic emulsifiers (i.e. soluble in petroleum) promote the formation of
water in oil emulsions. Hydrophobic emulsifiers include resins dispersed in
particle form within soot, clay and other substances.
• Petroleum emulsions can be characterized using properties such as viscosity,
dispersion, density, electrical properties and stability. The viscosity of petroleum
emulsion changes within wide ranges and depends on the viscosity of petroleum,
temperature, and amounts of petroleum and water.
• Petroleum emulsions that are disperse systems have unusual properties under certain conditions,
i.e. they are Newtonian liquids. Thus, petroleum emulsions like all Newtonian liquids can be
characterized by an effective viscosity.
• The sizes of droplets can change depending on the physical-chemical properties of petroleum and
water as well as the conditions of emulsion formation. Sizes range from 0.1 micron up mm.
Disperse systems which consist of droplets of the same size (single diameter) are referred to as
mono- disperse. On the other hand, systems that consist of droplets of different sizes are called
poly-disperse systems. Petroleum emulsions are poly-dispersed systems.
• The critical droplet size that can exist in the flow at a given thermodynamic mode is determined
by the velocity of movement of the mixture of water and petroleum, interfacial tension between
the phases and pulsation of flow.
• In the turbulent flow regime, caused by non-uniformity of pulsation and variable cross section of
pipeline, the existence of droplets of various diameters is possible. Fine droplets that move in the
section of pipeline of lower velocity gradients and smaller pulsation tend towards agglomeration,
whereas those that move in the zones of high velocity gradients and large pulsation tend towards
splitting. The presence of additional factors (such as heating, addition of emulsifier, etc.) under
certain hydrodynamic conditions can lead to the separation of the emulsion phases in the
pipelines.
• A higher degree of emulsion stability depends on the structure of the compounds that constitute
the protective layer formed on the surface of the droplet. The emulsifier adsorbs on the surface
of the droplet and covers it with a preserving layer thereby stabilizing the droplet. This layer
prevents droplets from merging with each other (i.e. promotes emulsion formation and stability).
Separation of Water-Oil Emulsions
• The process sequence of breaking petroleum emulsions follows the consecutive steps:
agglomeration and flocculation of droplets, destruction of the protecting layers,
coagulation of the droplets of the disperse water up to a size sufficient to further merge
by the influence of gravity, and then falling down to the bottom of the separator. If the
droplets have sufficient energy for the destruction of the protecting layers to occur, then
the droplets will merge.
• A number of technological methods are applied for petroleum drying. The choice of
method for petroleum drying and performance scheme employed substantially depends
on the amount and condition of water present.
• Water contained in crude petroleum appears in free form, i.e. non-dispersed form, in
some cases. Such water can be removed from petroleum directly by coagulation.
• More often however, water in crude petroleum is present in its dispersed form, emulsion
of water in oil.
• There are two versions of this emulsion: mechanically non-stabilized and
stabilized by interfacial-active substances. This distinction for emulsions is
essential for petroleum drying. Water from non-stabilized emulsions can be easily
separated by the usual settling method or by settling with moderate heating.
• Settling, centrifugation and filtration are mechanical methods for petroleum drying.
• Settling is applied if unstable emulsions are processed. Here, the droplets are stratified due to the
difference in the densities of the materials in the phases.
• The droplets' settling speed for designing separators is calculated using the formulas
• These equations imply that the major factors that influence the efficiency
of emulsion separation are:
• Densities of the phases in the emulsion (essentially, the difference in
density of the phases is responsible for gravitational separation);
• The viscosity of the emulsion phases, especially the viscosity of the
continuous phase (this is a very significant factor and affects efficiency of
petroleum drying by affecting transport of droplets or particles through the
medium);
• Diameter of droplets or particles of the discontinuous phase (this factor is
very important because the settling speeds of the droplets or particles
grow proportionately to the square of their diameters);
• The acceleration of the droplets or particles is due to their presence in the
natural gravitational field. The value of the acceleration is approximately
9.8 m/s2
• The area available for settling.
These factors can therefore be used in design to improve the efficiency of emulsion
separation. The favourable ways to apply these factors are as follows:

• Increase of temperature of the emulsion. This reduces the viscosity of the emulsion
phases,

• Reduces the interfacial tension between the phases (the thermal methods of petroleum
drying are based on this principle);

• Increase of droplet sizes of the discontinuous phases via various methods such as use of
chemicals

• Increase of the settling speed of the droplets by replacing the natural gravitational force
by the more powerful centrifugal force.

• Increase of the useful settling area without increase of the general area of separator.
 Mechanical Petroleum Drying
• The most basic method in mechanical petroleum drying is gravitational
settling. There are two types of settling modes. batch and continuous.
• Cylindrical separating tanks (settling tanks), similar to petroleum storage
tanks, are usually employed as batch separators. Crude petroleum
intended for drying is pumped into the tank through the distribution
pipeline. After filling the tank, the content is allowed to stay for a
predetermined period known as settling time. The water then settles to the
bottom section while petroleum floats on the top section of the tank.
• In the case continuous separation, two types of separators can be
distinguished: horizontal and vertical continuous separators. Horizontal
separators are subdivided into longitudinal and radial. Longitudinal
horizontal separators can be rectangular or round depending on the
geometry of the cross section.
Thermal Petroleum Drying
I this case, the petroleum for drying is heated up before the settling step. Heating
destabilizes the "water in petroleum" emulsion and promotes the merger of fine
droplets of water into larger droplets. Usually, protection layers consisting of
asphaltene-resinous substances and paraffins are formed on the emulsion surface
of water droplets. At normal temperatures, these layers create a very stable
structure that prevents the merging of droplets. By increasing the temperature, the
viscosity of the materials that form the protective layer is considerably decreased.
This leads to a reduction of the stability of the disperse structure, thereby
facilitating the merging of the water droplets. Besides, the viscosity of petroleum is
lowered as a result of heating. This promotes the acceleration of the water
separating from petroleum by settling. Thermal methods alone are applied rarely in
industry but they are used in combination with settling.
Chemical Methods of Drying
• The chemical drying methods are widely employed in the modern petroleum industry for
petroleum drying. The fundamental principle of such methods is the destruction of the "water in
petroleum" emulsions by using chemical additives. Many types of such additives have already
been developed in the industry. The efficiency of chemical petroleum drying depends
substantially on the type of additive used.
• Like in other combined petroleum drying methods, chemical drying is followed with settling of the
emulsion under the influence of gravity.
• Most effective additives are formed by reaction of ethoxylates. The additive solubility in water
in- creases with the lengthening of the ethylene oxide chain. If it is necessary, it is possible to
make these additives with hydrophobic properties by reactions with propylene oxide, i.e. there is
the opportunity to create various additives with different properties.
• The additives should dissolve well in one of the emulsion phases (in water or petroleum), i.e. they
should be hydrophilic or hydrophobic, in order to be able to destroy the protective film of the
water droplets. Also, they should be inert to metals, should not worsen the quality of petroleum,
should be economical, and should be of universal applicability with respect to use for various
emulsions.
• The sooner the additive is added to the emulsion of water in petroleum, the easier the
separation. For separation, however, just adding the additives to petroleum is not sufficient. It is
necessary to ensure the best possible contact between the additive and the water droplets.
Intensive mixing and emulsion heating can achieve this.
RECTIFICATION