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In the reservoir, crude oil is in intimate contact with formation water (connate) which is saline to varying degrees and, oil and water have various other minor substances in their composition which act as natural emulsifiers and fluid flow conditions bring about thorough mixing and dispersal of one phase in another i.e. forming EMULSIONS. Thus, the problem of emulsion requires timely resolution by proper method. Apart from dehydration, desalting and removal of basic sediment are to be attended to so as to make crude oil marketable (water of 0.5% to 2% or less and salinity < 8 ptb) depending on the sale price and contract specifications. Oil must be demulsified as water causes refining difficulties such as corrosion, coke deposition, foaming, pipeline transportation, tank corrosion, increased power consumption and equipment wear and tear because of increased viscosity and volumes with corresponding effects 2 on production equipment.
EMULSIONS
Emulsion - a mixture of two mutually immiscible liquids, one of
which is dispersed as droplets in the other & is stabilized by an emulsifying agent. Dispersed droplets are known as internal phase & liquid surrounding them is the external or continuous phase. Emulsifying agent separates the dispersed droplets from continuous phase & continuous phase from the dispersed droplets. In the oilfield, O&W are in 2 - phases and usually form a water-in-oil emulsion although occasionally the REVERSE or oil-in-water emulsion will form. Components of water-in-oil emulsions: Water - dispersed or internal phase Oil - continuous or external phase Emulsifying agent - stabilizes the dispersion
Three components themselves will not form emulsion unless there is enough agitation (disperse one liquid into another)
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Tight emulsion has small dispersed droplets which have considerable resistance to settling & is usually a stable emulsion
Loose emulsion is less stable than a tight emulsion because of the large dispersed droplets that tend to settle easily.
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Chemical demulsifiers rupture the tough skin of film surrounding a water droplet, thus allowing droplets to unite & settle.
Stability
amount of emulsifying agent. Stable emulsions may take weeks / months to separate if left alone in tanks without treatment whereas unstable emulsions may separate relatively in no time into clean O &W phases. Pure water & pure oil will never form an emulsion no matter how much agitation is applied as these dislike each other intensely. Therefore, if confined in the same container, they will quickly find a state of existence which gives the least contact or the smallest interphase area. A drop of water in a body of oil will take the shape which gives least surface area sphere. Also, water drop will squeeze itself in as tightly as possible to reduce its size & therefore its surface as much as possible. Measure of such a drop shrinking force is called Surface Tension. Material at new surface which is in contact with gas (or air) or another immiscible liquid as the case with O&W and this is known as interfacial tension
The surface tension of water at 20 C is 73 dynes/cm whereas that of most organic liquids is about 28 dynes/cm & this varies from 20 to 30 dynes/cm for crude oil & water. When oil & water are vigorously mixed, both types of emulsions are formed, but primarily the minor phase tends to become dispersed. Both type of emulsions tend to resolve and the surviving type (O/W or W/O) depend largely on the nature of stabilizer and the phase ratio. Formation of emulsion involves creation of enormous areas of interphase with attendant free energy supplied by agitation of pumps, friction in line or pr. drop through valves. Foe example, in half a gallon of oil a 1% emulsion consists of 0.0001 inches in diameter, these will be about 2 trillion of them & total area of interphase will be about 400 sq. ft. which can gather considerable amount of stabilizer or dust. In prime system of distilled water & pure HC (as Hexane) this free energy tends to subside and the drops collide to form free water. When the drops meet & unite, larger drops thus formed have less surface area than the sum of surrounding surface areas of the smaller drops. So in keeping with the desire of the water phase to find a state of existence giving the least surface area, drops will continue to unite until they have become one large drop or body.
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Normal oilfield emulsions consist of an oil continuous or external phase, and water dispersed or internal phase
Where high water cuts exist with low salt content & an emulsifying agent is present in the water phase, it is possible to form reverse emulsion with water as continuous phase & oil droplets as internal phase. Also electrical charges play strong role in stabilizing. These charges can be maintained in waters of low conductivity or low salt content. As the salt content increases, type of emulsion becomes less stable since the charges on oil particles can bleed off & they can then more readily unite. With the emulsifying agent in water, it tends to surround oil particles & trap them. Induced emulsions which are deliberately created for processing. Dual (or complex) emulsions also form in low gravity, viscous crudes. These contain water as external phase & have an internal water phase in the dispersed oil. Vast majority of oil treating systems deal with normal emulsions.
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Types of Emulsions
+-------------------+-------------------------------+---------------------------+ Normal Induced Invert Dual I (multiple) I Deliberately promoted, Oil in water systems single
as for Desalting crude oil encountered in including both Refinery waste Disposal types & Effluents, invert muds
Real
Pseudo
Unstable prone to resolution, if given adequate time or by simpler methods as centrifuging etc.
Multiphase flow leads to greater emulsification on account of intimate mixing (G-O-W) and dispersion.
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Emulsifiers
To form an emulsion the system must have presence of water & oil, agitation and also an emulsifying agent which has a surface active behavior. Some of the elements have preference for the oil, and others are more attracted to water. An emulsifier tends to be insoluble in one of the liquid phases whereby concentrating at the interphase. It can act in one or more of the following manners: Decreases the interfacial tension of water droplet, thus causing smaller droplets to form which take longer to coalesce into larger droplets, which can settle quickly. Forms a viscous coating on the droplets that keeps them from coalescing into larger droplets when they collide. Emulsifiers may be polar molecules, which align themselves in such a manner as to cause an electrical charge on the surface of droplets. Since like charges repel, two droplets must collide with sufficient force to overcome this repulsion before coalescence can occur. Normally occurring surface active materials found in crude oil (asphaltines-general term applied to a large variety of high MW compositions containing sulpher, nitrogen, oxygen & metals etc.) serve as emulsifiers. Paraffin's, resins, organic acids, metallic salts, colloidal silts & clay and asphaltenes are common emulsifiers in oilfields. Drilling muds & workover fluids are also sources of emulsifying agents (EA).
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Emulsifiers
.contd. Type and amount of EA has an immediate affect on emulsions stability. Temperature history of emulsions is equally important as it affects the formation of paraffins & asphaltenes. Speed of migration of EA to the oil/water interphase and behavior in terms of strength of interphase bond are important factors. Emulsion treated soon after agitation or creation of paraffins & asphaltenes can be less stable and easier to treat if the migration of emulsifier is incomplete. Aged emulsion may be difficult to treat. Normally lower the crude viscosity & lighter the crude the more rapid is the aging process.
Therefore, early treatment may be a lesser factor in treating low viscosity , high API gravity crudes.
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DEMULSIFIERS
A demulsifier is effective in resolving emulsions through following four main actions: - Strong attraction to O-W interphase - Flocculation - Coalescence - Solid wetting Demulsifiers are similar in nature to emulsifiers and are surface active agents with certain built in properties which make them effective in disrupting the effect of EA. Action is all at water-oil interphase so it must get there to do its job. Faster it gets there, better job it will do. Since the emulsifier is fairly concentrated at the interphase and creates an hindrance to demulsifier. Therefore a good demulsifier must have a good built-in ability to migrate quickly through the oil phase & compete against large odds for its place at interphase.
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Once demulsifier reaches interphase, it proceeds to its major action of flocculation. A good demulsifier, concentrated at the surface of water droplet, has a strong attraction for other droplets in same condition. By this mechanism , large bunches of drops are joined together. When magnified, they take on appearance of bunches of fish eggs. The oil takes on a bright appearance since the smaller water droplets are nolonger dispersed throughout the oil to diffuse light. Characteristics of demulsifier to produce the joining of droplets does not disrupt the continuity of the emulsifier film but just adds to it. If the emulsifier has certain weeknesses, this flocculation force may be sufficient to cause complete resolution of emulsion. However, in most cases further action is necessary for the water droplets to unite & become large enough to settle out. This action of uniting water droplets is called Coalescence.
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DEMULSIFIERS
-------- contd.
Good demulsifier must not only be able to flocculate water particles but also be able to disrupt films surrounding them & allow them to unite. Such disruption removes the barriers or opens the doors. The strong natural desire for water to seek its kind is reestablished. Since the particles are all closer together because of flocculation, this door opening process results in a very rapid growth of water drop size & water separation. In most crude oils , solids such as iron sulphide, silt, clay, drilling mud, parrafin etc. complicate the demulsification process. They tend to collect at interphase & contribute significantly to emulsion stability. Often such solids are primary stabilizing agents / materials & their removal is necessary to achieve satisfactory treatment. For removal from interphase, these solids can be dispersed in the oil or they can be water wetted & removed with water. If, dispersed in oil, emulsion may be treated, but the solids will still remain as a contaminant in oil. Therefore it is desirable to remove the solids with water. Paraffins & organic solids are exception to this as these can be recovered in refining process.
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DEMULSIFIERS
-------- contd.
Same type of action is used in either oil or water-wetting solids, only the chemical is different. In both cases, chemical has one end which is strongly attracted to the solid & therefore forms a coating on it. The other end has either a strong attraction for water or for oil & therefore will carry solid particles in that liquid. It is very rare that a single chemical will produce all the actions of a demulsifier. Mostly two or more structures are blended to give the necessary combination of actions. Selection of demulsifier is made with process system in mind. As the field conditions change, the chemical requirements change. Seasonal changes bring paraffin induced emulsion problems. Workovers contribute to solids content, which alters emulsion stability. So, no matter how satisfactory a demulsifier is at one point of time, it cannot be assumed that it will stay over the life of field.
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Means of treatment for dehydration of crude oil are: Gravity separation Temperature effect (heat) Chemical destabilization Electrical treatment (electrostatic coalescers). Gravity separation: Most of the oil treating equipment rely on the gravity to separate water droplets from oil continuous phase, because water droplets are heavier than the volume of oil they displace. However gravity is resisted by a drag force caused by droplets downward movement through the oil. When the two forces are equal, a constant velocity is reached, which can be computed from Stokes law as :
Vt
From Stokes law it can be concluded that : Larger the size of water droplet, larger the square of its diameter and thus, the greater its downward velocity. That is, the bigger the droplet size, the less time it takes for the droplet to settle to the bottom of the vessel and thus it is easier to treat oil. Greater the difference In density between water droplet and oil phase, the greater the downward velocity meaning, the lighter the crude, easier to treat oil. If crude gravity is 10o API and the fresh water, the settling velocity is zero, as there is no gravity difference. Higher the temperature, lower the viscosity of oil and thus the greater downward velocity, that is easier to treat oil at high temperature than at low temperature.
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COALESCENCE
in treating oil system is time dependant. In dispersion of two immiscible liquids, immediate coalescence seldom occurs when two droplets collide. If the droplet pair is exposed to turbulent pressure fluctuation, and the kinetic energy of adhesion between them, the contact will be broken before coalescence is completed. Deep layer gravity settler experiments indicate that the time to grow a droplet size due to coalescence can be estimated by the following equation: t = --- X 6 dj - (do)j ------------- ks
where d-o d ks j
= = = = =
initial droplet size final droplet size vol. Fraction of oil phase empirical parameter for particular system Empirical parameter always >3 and dependant on the probability the droplets will bounce apart before coalescence occurs.
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When the energy of oscillations is very low so that bouncing of droplets approaches zero, j approaches 3. Assuming a value of 4, the min time required to obtain a desired particle diameter can be expressed : t = --- X 6 d4 - (do)4 ------------- ks
Assuming, do is small relative to droplet size we wish to grow by coalescence in our gravity settler, then the equation can be approximated : d4 -------------2 ks
t =
Following conclusions can be drawn : Doubling of residence time increases the maximum size drop grown in a gravity settler less than 19%. If the value of j is > 4 the growth of the droplet diameter will be even slower.
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More dilute the dispersed phase, the greater the residence time needed to grow particle size. That is, coalescence occurs more rapidly in concentrated dispersions. That is the reason that oil is water washed by entering in the treating vessel below the o/w interface in most treaters. Flocculation and coalescence therefore occur most effectively at the interface zone between oil & water.
Temperature (heat) Effects : Heating of incoming oil/water stream for separating the phase is in use in oil Industry from earlier days. The addition of heat reduces the viscosity of the oil phase thereby allowing more settling velocities (Stokes Law). It also has the effect of dissolving the small crystals of paraffin and asphaltenes and thus neutralizing these effects as emulsifier. Treating temperatures, usually range from 100o to 160o F. In treating the heavier crude the temperatures may be as high as 300oF. Heating causes a significant loss of lower boiling point hydrocarbons (light ends). This results in shrinkage of the oil, or loss of volume. The molecules leaving the oil phase may be vented or compressed and sold with gas, even if they are sold with gas, there will be probably a net loss of in revenue realized by converting liquids volume Into gas volume. Figure approximately shows the amount of shrinkage that may be expected. Thus heating makes the crude oil recovered more heavier and thereby decreasing its value.
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The demulsifier must also have an attraction for droplets with a similar condition, which make large droplets to cluster together which under a microscope, appear like bunches of fish eggs. The oil will be on brighter appearance since drops are no longer present to scatter the light rays. At this point the emulsifier film is still continuous. If the emulsifier, is weak the flocculation force ma be enough to call coalescence. This is not true in most cases and the demulsifier must neutralize the emulsifier and promote a rupture of the droplet interface film. This is the opener that causes coalescence. With the emulsion in flocculated condition the film rupture results in rapid growth of the water drop size.
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.contd.
Electrical Treatment (Electrostatic Coalesces) : Coalescing and collision of the small water drop dispersed in the crude can be accomplished by subjecting the water-in-oil emulsion to a high voltage electric field which induces dipole attraction between them. After coalescence, separation of phases are due to gravity. When a nonconductive (oil) containing a dispersed conductive big (water) is subjected to an electrostatic field, the conductive particles or droplets are caused to combine by one of three physical phenomena. * The droplets become polarized and tend to align themselves with the lines of electric force. In doing so the +ve and ve poles of the droplets are brought adjacent to each other. Electrical detraction brings the droplets together and causes then to coalesce. Droplets are attracted to an electrode due to an induced charge. In an AC field due to inertia small droplets vibrate over a larger distance than larger droplets promoting coalescence. In DC field, the droplets intend to collect on the electrodes forming larger and larger drops until they fall by gravity. The electric field tends to distort and thus weaken the emulsifying film. Whatever the actual mechanism, the electric field causes the droplets to move about rapidly in random directions, which increase the chances of collision with proper velocity, coalescence occurs.
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= Attraction force between droplets = Constant for system = Voltage gradient = Diameter of droplets = Distance between droplets
This indicates that the greater the voltage gradient the greater the forces causing coalescence. However, experimental data shows that at some gradient the water droplets can be pulled apart and a strong emulsion can be developed. For this reason electrostatic treaters are normally equipped with mechanism for adjusting the gradient of the field.
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Photos clipped from a movie sequence in an electric feasibility test cell to determine an emulsions susceptibility to break up in an electric field
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Photos start with a tight emulsion & proceed to breakup at lower end.
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Coil tube size ranges from 1 to 6 inch pipe, depending on heater size. The tube bundle usually is arranged so that it may be divided into two or more separate coils in case it is desired to flow more than one gas/oil stream through the same heater. Pipe or plate is used for the fabrication of the heating tube. The heat transfer rate varies from about 9, 000 to 15, 000 Btu/ft2 of heating tube surface. The stack furnishes the draft necessary to full combustion products through the heating tube. The stack diameter and length is best determined by experiment to give the highest efficiency for a particular heating tube design.
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..contd.
The burner is so positioned that the products of combustion are effective on the entire length of the heating tube. The raw gas is first mixed with air prior to entering the burner. This primary air (intake is through flame arrester) furnishes a large percentage of the total air required for complete combustion. Additional air required is supplied by the secondary air adjustment. With proper size burner orifice and supply gas pressure, the flame should be blue or blue-orange in color. Also, the flame should be on, or nearly on, the burner tip.
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To insure the pilot a continuous supply of gas, its source is located upstream from the temperature controller. Fuel gas strainer is placed upstream from the temperature controller and pilot supply connections. This prevents foreign particles from clogging orifices or lodging on the seat of the temperature controller. Liquids are also collected in the lower portion. Shell is designed to operate at atmospheric pressure. Dimensions of the shell are held to a minimum thus reducing both the quantity of heating medium required and heat loss to the atmosphere. Cover plates for the coil and heating tube are sealed tight to the shell to prevent leakage of the heat transfer medium. The fill cap serves as a liquid expansion chamber in addition to providing a surface for condensation of water vapor.
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Submerged or long nose choked (Figure) may be used on the inlet to the indirect heater coil. Its function is to increase the temperature difference between the gas and water, and thus a large mean temperature difference can be used in calculations. Since the choke is immersed in the hot water bath at the point of pressure reduction, the heated choke body and coil prevent hydrate formation. In order for the water bath heat to reach the gas in the tube bundle, it must penetrate several resistances to heat flow: the water film on the exterior surface of the flow pipe; the pipe wall and the inside gas film. These resistances depend on many factors: specific heat, density, viscosity, temperature of the gas and water, flow rates of the gas, tube wall thickness and conditions of the tube surface.
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The indirect heater should be inspected periodically to insure maximum performance. Scale on the heating tube and coil bundle lowers the heat transfer rate and should be removed. The water bath must cover all of the coils and its level is easily inspected through the fill connections. If liquid collects in the fuel supply gas line, it is advisable to use a liquid trap upstream from the reducing regulator to avoid burner and pilot malfunctions. Water for the heating medium should be as pure as possible and free of dirt, sand or other foreign material. Proper burner adjustment saves valuable fuel.
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TREATING EQUIPMENT
The most commonly used single well lease treaters is the vertical treater as shown. Flow enters the top of the treater into a gas separation section. Care must be exercised to size this section so that it has adequate dimensions to separate the gas from the inlet flow. If the treater is located downstream of a separator, this chamber can be very small. The gas separation section should have an inlet diverter and a mist extractor. The liquids flow through a down comer to the base of the treater, which serves as a free-water knockout section. If the treater is located down-stream 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 minutes retention time for both the oil and the water to allow the free water to settle out. This minimizes the amount of fuel gas needed to heat the liquid stream rising through the heating section.
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The end of the down comer 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 rises over the heater firetubes 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 the oil outlet. Any gas, flashed from the oil due to heating, flows through the equalizing line to the gas space above. Oil level is maintained by pneumatic or level operated dump valves. Oil-water interface is controlled by an interface controller.
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Differential Oil Control Chamber: The heated fluid transfers from the heating section over the fixed weir into a differential oil control chamber, which contains a liquid level control float. The fluid travels downwards to near the bottom of oil control chamber where the opening of the coalescing section distributors are located. Coalescing Section (Electrical Chamber): Heater treater uses a high voltage potential on the electrodes for coalescing of water droplets in the final phase of processing. The electrodes are suspended on the insulated hanger from the upper portion of vessel. The Ground electrode is furnished with solid steel hangers to ensure grounding with the steel of the treater. An externally mounted, oil immersed high voltage transformer is furnished to provide the power to electrodes. The transformer uses 240 volts in primary & supplied about 16500 volts in secondary. The high voltage secondary is connected to charged electrode through a specially designed high voltage entrance busing for insulation. Secondary is also connected to voltmeter & external pilot indicating lamp. The oil & entrained water enter the coalescing section from the differential control chamber through multiple, full length distributors. As the oil & entrained water come into contact with electrical field in the grid area, final coalescing of water takes place. The water falls back to the water area at the bottom and the clean oil continues to rise to the top, where it enters a collector and is discharged through the clean oil outlet control valve. ........contd.
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Desalination of crude oil For this reason total salt content of oil is a function not only of salt water remaining in oil but also of concentration of salt in that water. The water-soluble mineral salts are contained in water from most of the oilfields of the world. Salts are predominantly chlorides of sodium, calcium & their salinity varies usually in the range of 20,000 to 1,30,000 ppm equivalent of sodium chloride. The quantitative unit of salt measurement is usually pounds of chlorides per 1000 bbl of oil (ptb). Even if 1% water remains in dehydrated oil, with salinity of 20, 000 ppm of Nacl, 70 pounds of salt will be contained in each 1000 bbl of that clean oil. Any quantity above 10-17 lbs per 1000 bbls (p.t.b) is usually considered as causing problems in refinery processing.
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contd.
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Commonly used:
Washing & providing continuous phase water wash to reduce salinity Settling in tank to provide low velocity & increase residence time to allow free water to separate Mechanical treating by using centrifugal forces or other means to separate O, G & W. Reduce oil viscosity which enhances coalescence Cause thermal expansion of droplets which rupture film & help coalescence Aid dispersion of emulsifying agent into oil phase Create thermal current for water movement & collision Demulsifier weakens emulsifier envelope on water droplet Reduce interfacial tension Increase molecular attraction of emulsifier & enhances separation Water molecule forming a dipole is basis of electrostatic coalescence Causes coalescence of smaller to larger droplets Allows faster settling of drops
Heating to:
Chemical Treating:
Electrical Treating:
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