Crude Oil Treatment-Libre (1) CDSC

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Introduction
Rev: 0 Date: 28 Feb, 2000 Page: 1.1
1.
1.1
Introduction
Scope
The aims of this section of the Treatments Handbook are to provide a source of reference information on crude oil treatment for refineries intending to optimise, upgrade or expand their existing units, and to facilitate the transfer of the best design and operating practices throughout BP Amocos refineries. Experience from operating units has been included where possible. The Treatments Handbook will be updated periodically. Recipients are encouraged to suggest topics for inclusion in future updates, and to suggest where added detail or explanation would be helpful in the text. All comments and queries should be addressed to: Robin Sanders BP Amoco plc Chertsey Road Sunbury on Thames Middlesex TW16 7LN, UK
Tel: 44-(0)1932 763400 Fax: 44-(0)1932 762985 Email: sanderrh@bp.com
1.2
Crude Oil Processing
Crude oils are the raw material of all BP Amocos refineries. They are delivered into the crude storage tanks where they are held until needed for further processing. They are then fed through a series of heat exchangers and heater to the crude distillation unit (CDU), which is the first major processing unit in the refinery. All crude oils contain impurities to varying degrees and these impurities adversely affect refining processes by causing fouling, increasing corrosion rates and poisoning catalysts.
BP Amoco Treatments Handbook
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Introduction
The treatment of crude oil mostly consists of desalting (to remove as many of the impurities as possible) and adding chemicals (to alleviate the effects of those impurities which remain). Figure 1.1 shows a typical crude oil processing scheme, in which the desalter is placed in the middle of the heat exchanger train, in order to desalt at a carefully selected temperature. Chemicals are added at various locations, but typically before and after the desalter and in the CDU overhead stream. The desalter wash water may also be chemically treated. Figure 1.1 - Crude Oil Processing
CDU Overhead Crude Distillation Unit CDU Feed
Crude Storage
Cold Preheat Exchangers
Hot Preheat Exchangers
VDU Overhead
Desalter
Heater Charge Pump Water In Water Out VDU Feed Vacuum Distillation Unit
VDU Bottoms
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils
2.
Crude Oils
Crude treatment is a complicated process because of the infinite variety of crude oils their sources, their methods of production, the results of crude blending, the recycle of slops - and the manner in which they are handled and stored.
2.1
Crude Properties
There are basically two types of crude oil properties which are relevant to desalting: those which are to be modified by desalting, and those which affect the efficiency of desalting. The purpose of desalting is to remove undesirable impurities which can cause corrosion, erosion, fouling and catalyst deactivation in downstream units. The main impurities found in crude oil are: Chloride salts - NaCl, CaCl2, MgCl2 - in the form of brine or solid crystals. These undergo hydrolysis at temperatures above 540 C, 200 C and 120 C respectively, forming HCl which is the main cause of corrosion in the crude tower overheads section. Mg and Ca chlorides are the worst offenders because they hydrolyse at much lower temperatures than sodium chloride. Basic sediments - ash, sand & grit from the drilling process; insoluble salts e.g. FeS, FeO; scale e.g. CaSO4 - large inorganic particles 20-200 microns in diameter. These can cause fouling in heat exchangers. Filterable solids - very small insoluble inorganic solids 1-20 microns in diameter, which can cause erosion. Water - both free water and small droplets emulsified into the crude. Heavy metals e.g. Ni, V, Ba - usually contained in large organic complexes. Some metals cause catalyst deactivation in catalytic processing units. Typical crude impurity concentration ranges are as follows: Table 2.1 Impurity Soluble Salts as Na BS & W Basic Sediment Filterable Solids Iron content Units lb/1000bbl (mg/l)* vol % wt % lb/1000bbl (mg/l)* wppm
* 1 mg/l = 0.3503 lb/1000bbl (PTB). 1 PTB = 2.853 mg/l.
Concentration Light crude: <20 (<60) Normal Maximum: 40 (120) Maya crude: up to 120 (340) 1-2 0.01 - 1.0 30 - 120 (85 - 340) 1 - 120
Crude properties which affect the desalter performance are: Density (or gravity) - lighter crudes settle faster than heavier crudes. Crudes with an SG greater than 0.95 (<17 API) can be particularly difficult to treat. Viscosity - heavier crudes are typically more viscous. High viscosity makes it more difficult to atomise the crude, leading to poor mixing. It also adversely affects the coalescing of the droplets, making a longer settling time necessary. The viscosity can be reduced by increasing the temperature of the feed to the desalter. Asphaltenes - tend to occur more in heavier crudes, are surface active and therefore prevent the oil and water phases separating. The chemical treatment company BetzDearborn developed a correlation for San Juaquin Valley (SJV) crudes by doing a regression analysis on groups of properties. The company was interested in predicting how much demulsifier should be added to a given crude oil, but the demulsifier demand which they defined gives an indication of the difficulty of separating the oil-water emulsion. ISettle = / (API - 10) IAsph = (XA + XCC - 4.1 + (XNi + XV) /35) /3 (2.1) (2.2) (2.3) (2.4) (2.5) (2.6) (2.7)
ISolids = (XFS + XBS /24 + XFe /1300 + (XAl + XZn + XCu) /92) /4 XSCl = YCl - YNa - YCa (if >0, otherwise = 0) (if >0, otherwise = 0) (if >0, and (YCl -YNa)>0, otherwise = 0)
XSNa = YNa - YCl XSCa = YCa - (YCl -YNa) DD where: DD ISettle IAsph XSCl
= 1.11 ISettle + 153.9 IAsph - 8.6 XSCl - 51.6 XSCa - 412
= Demulsifier Demand (ppm) = Settling Index = Asphaltene Index = Excess chloride (meq/litre)
ISolids = Solids Index XSNa = Excess sodium (meq/litre), including minor amounts (<10%) of K XSCa = Excess calcium (meq/litre), including minor amounts (<10%) of Mg API XA XCC = Kinematic viscosity @ 100 C (cSt) = Gravity ( API) = Asphaltene content (wt.%) = Conradson carbon (wt.%)
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils XFS XBS XNi XV XFe XAl XZn XCu YCl YNa YCa = Filterable solids (wt.%) = Basic solids (wt.%) = Nickel content (ppm) = Vanadium content (ppm) = Iron content (ppm) = Aluminium content (ppm) = Zinc content (ppm) = Copper content (ppm) = Chloride content (meq/litre) = Sodium content (meq/litre) = Calcium content (meq/litre)
Equation (2.7) applies only to SJV crudes. In this case, the strongest influence is from the asphaltenes, while solids and excess Na had virtually no impact and do not appear in equation (2.7), the coefficients for ISolids and XSNa being zero. For crudes from other fields, the coefficients of equation (2.7) will vary.
2.2
Heavy Crudes
Heavy crudes, with gravity less than about 20 API (SG >0.93), can cause significant processing problems in desalters. Heavier crudes generally have: Higher viscosity - reduces the available mixing potential, stabilises emulsions and increases retention of solids. Higher density - reduces the gravitational driving force for water-oil separation. Higher conductivity - increases the power consumption and reduces the available electric field strength, reducing droplet coalescence efficiency. Higher level of undissolved salts, solids and heavy metals - greater emulsion and rag-layer stabilisation. Poor heat transfer properties resulting in lower available desalting temperatures - a general reduction in desalter efficiency. Higher surfactant contents, both naturally and from the use of advanced recovery techniques at the oilfield. This stabilises emulsions.
Figure 2.1 - Variation of Crude Oil Viscosity with Temperature

10
Viscosity (Centistokes)
1.0
36 API 30 API 22 API 16 API
0.1
0.01 70 120 170 220 270 320
Temperature (F)
Figure 2.2 - Relative Variation of Settling Velocities with Temperature for Light and Heavy Crudes
10000 9000 300
Relative Settling Velocity 30 API Crude
8000 7000 6000 5000 4000 3000 2000 1000 0
200
150
100
50
200
225
250 Temperature (F)
275
300
Heavier crudes generally contain higher concentrations of impurities containing atoms such as sulphur, nitrogen and oxygen. These atoms form polar molecules which act as surfactants and increase the conductivity of the crude oil. High viscosity, lower temperatures and higher crude conductivity act against coalescence efficiency; high BP Amoco Treatments Handbook
Relative Settling Velocity 16 API Crude
30 API, 5 micron droplets 30 API, 10 micron droplets 16 API, 5 micron droplets 16 API, 10 micron droplets
250
viscosity and high crude density reduce droplet settling velocities; higher salt and solids concentrations and surfactant levels caused by more severe recovery processes at the oil field and by higher natural surfactant content (e.g. polar molecules, asphaltenes, naphthenic acids), stabilise emulsions and reduce dehydration efficiencies. All of the above properties of heavier crudes combine to reduce the efficiency of the desalting process. In general, it is much harder to achieve the same desalting efficiency with a heavy crude as it is with a lighter crude and therefore heavy crudes represent a significant challenge to the refiner. Effective desalting may require: Multi-stage desalters. Aggressive chemical additive program. Optimised desalter operation, particularly mixing. Appropriate desalter internals and electrical grids. Blending of heavy crude with either a lighter crude or a lighter distillate fraction. Care must be taken with the last of these options because blending of a heavy, asphaltenic crude with a light, paraffinic fraction can cause the asphaltenes in the heavy crude to precipitate out, stabilising rag-layers and emulsions and increasing fouling rates in the preheat exchangers. In addition, blending may also increase the conductivity of the heavy crude significantly. High oil conductivity is undesirable in the desalters because it increases electrical power consumption: the drawn current increases and the electric field strength falls, thus reducing the coalescing efficiency. In the worst case the transformers may trip completely causing a major operational upset.
2.3
Crude Storage
1. Blending Mixing of crude oils with different properties can result in both beneficial and adverse effects on desalting. Switching the feed from one storage tank to another can introduce crude blends for which the desalter was not designed. For example, mixing a highly paraffinic crude with one high in asphaltenes can result in a very stable emulsion in the desalter. Switching of tanks should be done in such a way that the change over from one crude to the other is done slowly over several hours so that, if necessary, the desalter performance can be retuned. Sometimes, crudes are mixed deliberately to improve the properties of one of them. For example, mixing a light crude with a very heavy crude will reduce the settling index (see section 2.1) of the heavy crude. Of course, other properties may suffer, and the compatibility should be checked in the laboratory. When different crudes are mixed in the same tank, they should be thoroughly mixed together for at least 8 hours, and then left for a further 24 hours for water and solids to settle out. 2. Slops Extract from the Distillation Handbook, vol.3, section H.2.29 (rev.1): BP Amoco Treatments Handbook
The reprocessing of slop oils produced from normal refinery operations often leads to a high solid feed to the desalter. Also impurities and chemical species present in slops can act to stabilise the emulsion making it harder to break. This can result in a higher exit BS&W, and oil undercarry to the effluent water. Slop oil processing should be monitored and the desalter operation adjusted to handle the changes in feed. The addition of more demulsifier, or lower mix valve pressure drop can aid in reducing the stability of the emulsion. The addition of a solids wetting chemical may also be considered. Gasoline with oxygenated additives is also best not routed to the CDU because the oxygenates tend to end up with the water phase from the desalter and result in increased BOD to the effluent treatment plant. Slops containing amines will reduce desalter efficiency as they have a detrimental effect on the droplet coalescence. Amines will react with organic acids to form salts, which will migrate to the oilwater interface and act as surfactants. This will stabilise the emulsion. If slops must be routed to the desalter, they should be injected slowly and continuously into the crude charge line. 3. Water Draining Allow crudes to settle for at least 24 hours. Just before charging to the CDU drain as much water as possible. This is especially important if the desalter is out of operation, or being bypassed for any reason.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters
3.
3.1
Desalters
The purpose of Desalting
The primary objective of desalting is to remove as much as possible of the soluble chloride salts from the crude oil. The process also reduces the basic sediment & water content (BS&W) of the crude, and to some extent will reduce the level of the other impurities present. The process of desalting consists of mixing a small quantity of water (approximately 5% of the crude volume) with the crude oil to form an emulsion, then breaking the emulsion into two liquid phases in a horizontal vessel - the desalter. This process, when performed correctly, transfers the bulk of the impurities into the water phase, leaving a purified oil phase which can then fed to the crude distillation unit, (see figure 1.1). One of the main problems of desalting is the separation of the oil-water emulsions. Good mixing of the oil and water is relatively easy to achieve. If the mixing is too good, a stable emulsion can form, which is nearly impossible to separate. On the other hand, if mixing is not good enough then all the impurities will jot be removed from the crude oil. An efficient desalting operation is one in which the right balance is achieved between mixing and breaking the resulting emulsions. Many factors contribute to the problem and its solution, including: Crude oil properties Water purity Desalter design Desalter operating conditions Addition of chemicals The benefits of effective desalting are significant, both in terms of improved refinery operation and, indirectly, in terms of profits. They can be summarised as follows: Minimised corrosion and fouling - removes the impurities which are the cause. Greater throughput and capacity - lower crude water content increases the CDU efficiency and capacity. Smoothed changes between crude runs - downstream units see a more uniform feed. Improved product quality - prevents entrainment of salts and solids. Reduces contamination - removes sodium and other metals, which can act as catalyst poisons and cause upsets in downstream units. Reduces equipment erosion - by removing solids. This results in lower maintenance costs. Extends run lengths - by decreased deterioration of equipment and catalysts. This leads to greater profits. BP Amoco Treatments Handbook
3.2
Process Description
The water naturally found in crude oil is present in small droplets finely dispersed within the oil phase. The bulk of the impurity salts and solids are contained within these water droplets, but significant quantities of insoluble solids and salt crystals exist as oil-coated particles in the oil phase. The filterable solids and salts concentrate at the oil-water interface where they act as surfactants, increasing the surface tension of the droplets and making it harder for them to coalesce. Wash water is intimately mixed into the crude oil with a mix valve or static mixer upstream of the desalter vessels in order to dilute the impurities and extract the oilphase solids and smaller water droplets into the water phase. The resulting water-oil emulsion is fed to the desalter vessels where a combination of long residence time, electric field and demulsifier additives are used to improve the rate of gravitational settling of the water droplets from the oil phase. The desalted oil, containing much less water and impurities, is removed from the top of the vessel. The wash water is removed from the bottom of the vessel as effluent brine and sent to a waste water treatment system. Desalter systems can either contain a single or multiple desalting stages. Typical PFDs for these systems are shown below. Figure 3.1 - Single Stage Desalter System
Desalted Oil to CDU Transformer Demulsifier
Electric Field Grids
Preheat train
Mix Valve
Feed Distributor
Crude Oil
Desalter
Wash Water (eg from SWS)
Brine Effluent to Treatment
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters Figure 3.2 - Two Stage Desalter System
Demulsifier Preheat Train Crude Oil Effluent Brine to Treatment Wash Water (eg from SWS) Demulsifier (if needed)
Desalted Crude to CDU
Mix Valve
First Stage Desalter
Second Stage Desalter
Second Stage Brine to First Stage
As shown, the wash water may be added before or after the preheat train, but not (as some do) into the suction of the crude charge pumps (see section 3.5.1).
3.3
Desalter Design
The mixing of the crude oil with water forms two basic types of emulsion: oil continuous and water continuous. The primary method of method of separation is by gravity settling. This is accelerated by different methods aimed at coalescing the small droplets into larger ones. The oil continuous emulsion is coalesced using a high voltage electrical field. Chemicals and temperature are used to assist both emulsions to coalesce. 4. Gravity Settling The settling velocity for water droplets under gravity is given by Stokes Law: V= gd 2 ( w o ) 18 or or or or or ft/sec ft/sec2 ft lb/ft lb/ft.sec
3
(3.1)
where, using consistent units, V = settling velocity, m/s g = gravitational constant, m/s2 d = droplet diameter, m w & o = density of bulk water and 3 oil phase, respectively, kg/m = oil viscosity, kg/m.s
Experiments by the Petrolite Company have shown that for a typical light crude the water droplet sizes vary between 0.5 and 17 microns (m) in diameter, with an average of 3 microns. The settling velocity for droplets of this size under gravity is very low (~3 mm per hour) so that very long residence times would be needed to separate the water from the oil unaided. BP Amoco Treatments Handbook
The density difference between the oil and water phases is the driving force for gravitational separation. The difference is greater for light than for heavy crudes and can be increased slightly by increasing the operating temperature. Similarly, the oil viscosity can be reduced by operating at higher temperatures, thus increasing the settling velocity. However, the maximum temperature is limited by the available preheat and by the need to prevent vapour formation at the operating pressure. The water droplet diameter is the key variable in determining the settling velocity, and therefore the efficiency of water removal from the crude, because it is the only variable over which we have significant control. In addition, the settling velocity is much more sensitive to the droplet diameter than the other variables. A small increase in the droplet size leads to a large increase in the settling velocity. The desalting process employs this principle to improve significantly the efficiency of separation between water and crude oil. Figure 3.3 - Variation of Settling Velocity with Droplet Diameter
20 18
Relative Settling Velocity
16 14 12 10 8 6 4 2 0 1 2
SG SG SG SG
0.95 0.90 0.85 0.80
At Constant Viscosity
10
Relative Droplet Diameter
5. Electric Field Droplet coalescence is much improved by the application of a high potential electric field across the desalter vessel. The electric field acts on the polar water molecules inside the droplets and induces attractive dipole forces. The force between pure water droplets is given by: 6 KE 2 d 6 F= z4 where, F = coalescing force, (3.2)
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters K E d z = emulsion dielectric constant (~6-8), = field strength, (voltage) = droplet diameter = droplet centre separation, (distance).
The force, and therefore rate of coalescence, is greatly increased as the droplet size increases, the droplet separation falls and the applied voltage increases. By relating the average droplet separation to the volume fraction of water in the crude, we can determine the relative coalescing force between droplets as a function of the wash water addition rate. Table 3.1 Brine Concentration vol. % 5 1 0.1 Average Droplet Separation (diameters) 2d 4d 8d Coalescing Force d2/16 d2/256 d2/4096
Figure 3.4 - Influence of Wash Water Addition on Coalescing Force

1000
Relative Coalescing Force
100
10
1 0.1 1 10
Wash Water Addition Rate (Vol%)
There is a maximum field strength limit beyond which the shear forces on the droplets become large enough to tear them apart, given by:
Emax C where Emax C d
(3.3)
= the max field strength, = a constant, = the droplet diameter = the droplet surface tension.
Efficient desalter operation is therefore a compromise between having a high enough applied field strength to cause rapid droplet coalescence and low enough not to break up and redisperse the larger droplets. Typical field strengths used lie between 0.5 - 1.2 kV/cm, corresponding to applied voltages of 12 - 35 kV, depending on the emulsion conductivity and desalter layout. Table 3.2 was presented by BetzDearborn at an AIChE meeting in New Orleans in 1998. It shows typical design values for the flow of oil and power requirements per unit area of the electric grid. The grid area is defined as the horizontal area of the lower grid.
Table 3.2 - Typical design specifications for desalter grids.
Crude gravity - API 12 15 20 25 30 35 40
Temperature - F 300 290 270 260 250 240 230
Oil flow - BPD/ft2 20 50 100 150 175 200 250
Power - kVA/ft2 0.6 0.5 0.3 0.3 0.2 0.1 0.1
6. Associated Hardware
Level control
There are a number of different technologies available for level control of the interface layer in the desalter. Each method is normally backed up with a system of five or more tricocks or a swing arm sampler for checking of meter accuracy and for taking samples of the rag layer. Other devices include displacement floats, capacitance probes, energy absorption probes and nucleonic level detectors. The latter three are the most easy to automate into a control loop. Regular checks of the instruments by sampling for the interface using tricocks is recommended. The control of the level is usually achieved using flow control on wash water addition based on crude charge rate, using the interface level to adjust the effluent water flow.
Table 3.3 - Level Controllers

Level device Displacement float Used in Auto? Yes Advantages Simple mechanical device Disadvantages i) requires manual calibration for different crude slates ii) not suitable for heavy crudes i) can get confused by emulsion layer ii) susceptible to fouling build up of asphaltenes or paraffins can be confused by sediment layer good for heavy crudes Comments Often found to be unreliable, though not in all services. Recommended as a back-up for some other measurement device.
Capacitance probe
Yes
i) very sensitive ii) can cope with crude gravity changes
Yes (1)
Admittance probe
Yes
i) insensitive to crude density changes not susceptible to fouling
Yes (1)
Energy Absorption
Yes
needs careful tuning
Also known as AGAR probes, is microwave based
Yes (1)
Differential Pressure
Yes
Can be installed external to vessel
i) prone to
plugging
No
ii) sensitive to
crude density changes
Note (1). It is good practice to use two level measurement devices. The displacement float provides a good back up to the other methods.
Rag layer draw
It is good practice to be able to draw the rag layer from the desalter by its own drain line or as a rundown via the tricock system. This allows the flexibility of removing a stable emulsion layer should it form and prove to be unbreakable by conventional desalting techniques.
Mixing device
A valve is the preferred choice for mixing oil and water. This ensures good mixing whilst offering controllability. The adequacy of mixing is a function of the pressure drop across the valve. Pressure drop is normally in the range of 0.5 to 2 bar. Some manufacturers suggest the use of double-port mixing valves which allows more intimate mixing to be achieved. However, this can lead to the formation of an over-stable emulsion and single-port mixing valves are considered adequate for most services.
Static in-line mixers offer a solution when the crude preheat train is hydraulically limited and pressure drop has to be minimised. The static mixer can provide intimate contact between the oil and water phases at lower pressure drops than mixing valves. However, the operator has no control over the mixing as the pressure drop cannot be varied. Static in line mixers should therefore only be considered as part of a revamp under severe hydraulic limitations, and not as part of a new design. Electrical equipment The electrical field used in a desalter is typically AC. The use of a DC field could lead to electrolytic corrosion within the vessel and DC power supply is more expensive. However, NATCO, produce a DC desalter, claiming that direct current fields are more effective than those using AC. Regardless of field type there is an upper limit to the field strength which should be employed. This is best advised by the desalter manufacturer. Above a critical level the electric field will cause water droplets to break up as they become heavily distorted. Transformers A desalter requires a transformer to step up the available voltage to that required to give the correct field strength in the desalter. The required field strength depends on the emulsion conductivity and emulsion location in the vessel. A typical desalter would operate at 0.5 to 1.2 kV/cm, which corresponds to a need for a 12 35KV supply. Grids The grids, or electrodes, are the devices between which the electric field is applied. The layout and the number of grids used varies between manufacturers, and for different applications by any given manufacturer. The number of grids and so number of power units / transformer is normally a function of throughput. Low capacity desalters (< 30,000 bpsd) operate with a single grid. For larger units and difficult crudes three grids and three power units are recommended. This also gives some redundancy BPs experience in the North Sea with a Petreco Bilectric desalter is that the failure of one grid and transformer out of three had minimal effect on desalter performance. The grids can also be single-, two- or three-phased. Single-phase systems use one live and one "ground" grid. In these systems there is an intense field between the girds and a less intense field between the bottom grid and the water since the vessel acts as the ground. Two-phase systems use two grids, but both are live. The phase difference of 180 degrees increases the voltage gradient between the grids to twice that of the transformer outlet. Three-phase systems use three grids; each is 120 degrees out of phase with its neighbour. The voltage gradient is three times the transformer outlet. High capacity desalters (> 100,000 bpsd) should use a three-phase system.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters Vessel (residence time)
Manufacturers disagree about the important of residence time in the BS&W and salt removal of the oil. However, there is agreement that residence time is an important criterion in ensuring low oil undercarry with the effluent water. Significant residence time requires a larger vessel but this has the additional benefit of giving the operator a longer time to respond to, and take remedial action for, potential process upsets such as a water slug in the feed. Distributor The distributor provides distribution of the emulsion from the mix valve along the entire length of the desalter vessel. The type of distributor and its position within the vessel relative to the electrodes varies with the type of the desalter. 7. Wash Water Addition Wash water is mixed with the crude oil at between 3 - 8% by volume of crude, either just before the desalter tank itself or upstream of the preheat exchanger train. Efficient mixing is necessary to ensure adequate contacting with the oil-phase and results in the formation of an emulsion. A rag layer is formed inside the desalter vessel where the high concentration of solids at the oil-water interface gives the appearance of mud. The increase in water volume has several benefits: The overall concentration of salts and impurities in the existing brine droplets is reduced. The dilution of these surfactant agents at the interface decreases the stability of the emulsion and promotes droplet coalescence. Any brine entrained into the desalted crude will also be more dilute. Solids and salts in the oil phase become water-wetted and are washed into the aqueous phase from where they can be extracted. Figure 3.5 - Desalter Dehydration Efficiency as a Function of Wash Water Addition Rate
Relative Dehydration Efficiency
Transformer Trip-Out
Wash Water Addition Rate
Rev: 0 Date: 28 Feb, 2000 Page: 3.10
More droplets are formed reducing the average droplet separation, increasing the likelihood of droplet coalescence and thus increasing the average droplet size and settling velocity.
The dehydration efficiency of the desalter as a function of the wash water addition rate can be plotted as shown in Figure 3.5. When the wash water addition rate is too low, on the far left of Figure 3.5, the dehydration efficiency of the desalters can be worsened. Below 3% the distance between droplets is too high for the attractive forces to promote coalescence and water is carried over with the crude oil. The optimum addition rate corresponds to the peak in the middle. The reduced droplet separation increases the rate of coalescence until water droplet carry-over is minimised. When the addition rate is too high, (over 8%) too many droplets make the emulsion too conductive. If, as a consequence, the water-oil interface rises too much until it extends between the electrodes, the unit becomes overloaded and the transformer trips out. The coalesced water droplets containing most of the original salts and solids accumulate at the bottom of the vessel and are drained and sent to waste water treatment. The desalted oil, containing significantly less water and impurities, is fed to the crude tower furnace. 8. Design limits and conditions Oil water separation relies on the buoyancy of the oil in the water phase for separation to be achieved. In order to achieve good separation the viscosity of the oil must not exceed a maxi-mum value. The viscosity can be manipulated by altering the operating temperature of the desalter. However, the temperature and pressure must prevent vaporisation of the oil. A suitable combination can always be found in the preheat train. The table below gives usual conditions and limits for desalter operation. Table 3.4
Condition Crude specific gravity Viscosity Temperature Pressure Wash water addition Wash water Mix valve pressure drop %vol on feed pH bar Units (SG) cSt degC Operating Range Below max. limit Below max. limit 100 150 no vaporisation 38 5.5 7.5 0.5 2 set by water capacity of vessel 8.0 when unbreakable emulsion formed Limit 0.95 0.975 15 160 ( set by insulators )
Rev: 0 Date: 28 Feb, 2000 Page: 3.11
The optimum conditions will be a function of a number of variables, mostly on the properties / quality of the crude charge: gravity of crude, viscosity curve of the crude, nature of the crude (naphthenic crudes emulsify easily), amount and quality of wash water, product quality required. 9. Typical Desalter Performance Desalter operation is a fine balance between a large number of conflicting variables and depends sensitively on the exact conditions. For example, maximum crude dehydration may come at the expense of increasing the oil content in the effluent brine. In general though, table 3.5 summarises some broad guidelines for desalter performance, and the targets should be easily obtainable with good operation. Table 3.5 Salt Out Salt Removal Solids Removal Iron Removal 0.2 - 2 PTB 90 - 99% 60 - 80% 50 - 75% Oil in Effluent Water BS&W Out Na Removal O/H Chlorides 0 - 1% 0.1 - 1% >95% 0.1 - 0.5 ppm per 1000 bbls crude
3.4
Proprietary Desalters
There are three major manufacturers of desalters: Axsia Howmar, Baker Petrolite and Natco. These companies offer comparable desalters though with slightly different design philosophies. The devices are based on AC operation although Natco also produce a DC variant. Differences between the Axsia Howmar and the Petrolite low velocity desalters are not highlighted but are small. The Axsia Howmar unit shown is generic and does not illustrate the full range of different arrangements which are possible with this unit. The designs produced by Axsia Howmar and Petrolite will vary because of their different views on the importance of residence time. Howmar believe coalescence improves with time, Petreco believe that coalescence is almost instantaneous and oil residence time is not an important factor. For specific mechanical details and layout reference should be made to the manufacturers brochures.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters Figure 3.6 - Typical Desalter Design
OIL POWER UNIT
Rev: 0 Date: 28 Feb, 2000 Page: 3.12
INTERFACE
GRIDS
WATER
EMULSION
MUDWASH WATER
10. Howmar and Petreco Low Velocity. Both Howmar (formerly HoweBaker) and the Petreco (now Baker Petrolite) offer low velocity desalters. Their designs vary because of their different views on the importance of residence time. Howmar believe coalescence improves with time and typically specify over 20 minutes crude oil residence time. Petreco believe that coalescence is almost instantaneous and oil residence time is not an important factor. The oil/wash water emulsion is fed into the desalter vessel below the grids. This minimises the power consumption of the vessel which will increase with the amount of water between the grids. A high intensity field exists between the electrodes, and a lower intensity field between the bottom grid and the water. The low intensity field removes the bulk of the water. Further coalescence occurs between the grids. The water oil interface is kept below the grids to avoid shorting. 11. Petreco Bilectric. The major difference between this desalter and those described above is the position where the emulsion is introduced into the desalter vessel relative to the electrode grids. The PETRECO BILECTRIC design of desalter feeds dual streams of oil-water emulsion between three sets of electrodes. The dual flow configuration gives it essentially twice the capacity per unit volume of vessel that vertical flow desalters have. The BILECTRIC design holds water levels high, near the middle of the vessel, to allow maximum residence time for oil to separate from effluent water. This increases the throughput for a given vessel. A stronger electric field is required because water in the emulsion (when fed between the grids) increases the power consumption. The oil-water interface is kept below the electrodes to avoid shorting the grids. With lower residence times there are more problems with water slugging and the BILECTRIC requires tighter level control.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters 12. Natco ElectroDynamic Desalters (EDD).
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By introducing novel features, Natco claim to offer a single stage desalter with the efficiency of multistage desalters and with a 25-30% higher capacity. BP Amoco experience is that an EDD is equivalent to 1.5 conventional desalting stages. Figure 3.7 - Natco Electro-Dynamic Desalters (EDD)
The EDD combines dual polarity electrostatic fields with electrostatic mixing and countercurrent flow. Unlike the Howmar and Petreco designs this desalter uses a DC field to aid coalescence as well as the traditional AC field. As it employs both fields it is sometimes referred to as an AC/DC desalter. Figure 3.8 - Dual Polarity Electrostatic Fields
The DC field is established by connecting both plates to the same terminal of the AC transformer with each plate charged during half of the AC cycle. The charge is maintained between cycles by capacitive storage - but because only one plate is charged at a time, no current can flow, which prevents corrosion problems. This patented design also creates an AC field between the edges of the plates and oil/water interface, and between the plates and walls of the vessel. Large droplets coalesce in BP Amoco Treatments Handbook
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the AC field outside the plates, while small droplets in the DC field pick up a charge from the nearest electrode and accelerate toward the oppositely charged plate, colliding with other drops, coalescing, and settling out. A load responsive controller supplies the electrodes with bursts of high followed by low voltage. Optimum field strength changes with drop size: large water drops coalesce in weak fields, but small drops require fields so strong that large droplets are shattered. This problem is solved by using electrostatic mixing to sweep across field strengths and mop up droplets of all sizes. Figure 3.9 shows how it works, as drops shatter and recombine. Each mixing cycle lasts 3-5 seconds, and a typical water droplet may undergo 10 - 15 cycles before completely settling out. Figure 3.9 - Electrostatic Mixing Cycle
Another difference is that the wash water injection is split: about 50% is introduced via a traditional external mixing valve, while the other 50% is introduced as dilution water at the top of the grids, counter current to the flowing oil (see figure 3.7). As the water falls through the grid, counter-current to the rising oil, it washes out the impurities. The remixing and recoalescing occurs a number of times to each droplet as it falls through the DC field, supposedly increasing the contacting efficiency between the wash water and the oil. The use of wash water in an external mixing valve will mean that traditional desalter contacting also occurs. The AC field between the electrodes and the water removes the bulk of the water from the electrodes before they can be subject to electrolytic corrosion. The AC field operates to some extent as in more traditional desalter.
3.5
Desalter Operation
13. Wash Water Feed Point
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The wash water feed to the first stage can be fed either in front of the preheat exchanger train or, more commonly, just before the actual desalter vessel. In multistage systems the wash water should be fed to the last desalting stage first, so that the water flows counter-currently to the oil, in order to maximise the water use efficiency. The advantages of feeding the first desalting stage wash water in front of the preheat exchanger train are: Dilution of solids and salt content in the crude tends to reduce fouling rates in the exchangers Longer contact time between the water and crude resulting in more efficient extraction of impurities Lower P required across the mixing valve Wash water heated with the crude avoiding the need for an additional water heater The disadvantages of this feed point are: Lack of control over the extent of mixing in the exchangers Still require a mixing valve before the desalter vessel as the degree of mixing in the exchanger train is too low Increased pressure drop through the exchangers Greater heat load on exchangers and reduced charge capacity Some people inject the wash water into the suction of the crude charge pumps when desalting heavy crudes, in order to promote good mixing. However, this is not recommended because there is no control over the degree of mixing, and for lessthan-heavy crudes the intense mixing will inevitably result in the formation of an unbreakable emulsion. 14. Mixing The general consensus of opinion across the industry favours the use of high shear mixing valves just upstream of the desalter vessel for mixing. Static in-line mixers have also been used with some success, but the lack of control over the extent of mixing may be a problem, especially when changing crudes. The pressure drop across the mix valve controls the size of the water droplets produced and therefore the efficiency of contacting between the water and the crude. The pressure drop across the mixing valve is typically 5 - 30 psi, depending on the crude type, flow rate, etc. Lighter, less viscous crudes can withstand higher mix valve pressure drops than more viscous crudes before tight emulsions are formed. For very heavy crudes (14 API) pressure drops as low as 4 psi on the first stage and 7 psi on the second stage have been used, because in this case it is important to use only enough pressure drop to get good mixing. If the pressure drop is too low, too little mixing occurs and the wash water remains as large drops in the crude. These make poor contact with the emulsified brine droplets and solids and settle out rapidly. It may appear that the percentage of water removal is good but in fact very little of the impurities or water originally present in the crude are removed. BP Amoco Treatments Handbook
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If the pressure drop is too high, overmixing occurs and a tight emulsion of tiny water droplets is formed. Good contact is made but the droplets formed are so small that the rate of coalescence and settling is very low. Water carryover is inevitable and the desalted crude can contain more water than the raw crude. The extra water droplets increase the overall emulsion conductivity which reduces the electrical field strength, further reducing the rate of droplet coalescence. It is possible that the electrical grid may short out, resulting in extreme operational difficulties. Figure 3.10 - Influence of Mix Valve Pressure Drop
% of Original Salt in Desalted Crude
100 1.0
80 % original Salt % BS&W 60
0.8
Mostly Water
0.6
40
0.4
20
Mostly BS
Optimum Range 0.2
Increasing Mixing Pressure Drop
For optimum performance, the pressure drop across the mixing valve should be closely controlled. 15. Multi-Stage Desalting When more than one desalting stage is used, the wash water is fed to the last stage first (see figure 3.2). The effluent brine from this stage is then fed to the previous stage, and so on, so that the wash water effectively flows counter-current to the crude oil. Reuse of the wash water in this way significantly reduces the total volume of wash water required with very little reduction in desalting efficiency. Sources of wash water are discussed in Section 3.6. Increasing the number of desalting stages has a significant effect on the final salt content of the desalted crude oil, but less effect on the water content. As a result, two or more stages are required where the crude oil is expected to have a high salt content or when there are downstream conversion units whose operation is sensitive to salt levels, such as an FCCU. The presence of an RCCU, such as at SRC, where it is necessary to reduce the salt concentrations to very low levels, requires a three stage desalting system.
% BS&W in Desalted Crude
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters Table 3.6 Number of Desalting Stages Typical Desalted Crude Salt Concentration mg/l 1 2 3 <10 1-3 <1 lbs/1000 bbl <3.5 0.3 - 1 <0.35
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Typical Water Content % vol 0.2 - 0.3 0.2 0.2
16. Temperature Desalters operate most effectively at higher temperatures because: The solubility of surface-active agents (such as asphaltenes) increases, reducing their concentration at the oil-water interface. The oil-water interface becomes less stable and viscous, decreasing the resistance to coalescence. The oil viscosity decreases, improving the mobility of droplets and chemical additives, and increasing droplet settling velocities. The density difference between the crude and water increases, increasing settling velocities even further.
However, the variation with temperature of oil viscosity, oil and water densities are not always uniform, and considering equation 3.1 the temperature should be controlled so as to maximise the function (w - o)/. Desalters normally operate between 200 - 300F (93 - 150C), depending on the available heat from the preheat exchangers. Typical design temperatures are shown in table 3.2. Usually, the upper temperature limit is imposed by the materials of the bushings. 17. Pressure The desalter pressure is usually defined by other units in the system (such as the CDU pressure and pressure drop through the heaters). The only important aspect to consider is that no vaporisation of the crude oil occurs, since that would upset the gravity settling of the two liquid phases. 18. Residence Time Whether or not any particular droplet will settle out from the oil-water emulsion depends not only on its settling velocity but also the length of time it remains in the vessel. Desalter operation attempts to maximise the settling velocity in order to minimise the size of desalter vessel required to separate a particular flow. Residence time depends on the flow rates of water and crude, and the vessel dimensions (see table 3.2). Good BP Amoco Treatments Handbook
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performance for a heavy (14 API) Californian crude resulted when the residence time at 315 F (157 C) was 1 hour in each of two stages. Increasing the flow through the unit will reduce the residence time and inevitably worsen the performance; decreasing the flow may improve performance but at the cost of lower throughput. Residence time may also be altered by adjusting the height of the oil-water interface, but this must be maintained below the lower grid. Raising the interface decreases the oil and increases the water residence times. This may reduce the carry-under of oil into the effluent brine. Lowering the interface increases the oil residence time and should improve the resolution of the emulsion, reducing water carry-over into the desalted crude. Efficient operation is a compromise between these two effects. Care must be taken though, because lowering the interface increases the distance between the lower electrical grid and the water, which decreases the electrical field strength across the emulsion layer. As a result, coalescence may be slower and more water may be carried over into the crude, contrary to expectation. 19. Mudwashing The insoluble solids contained in the crude oil are washed into the water phase in the desalting vessel and accumulate at the bottom of the tank in a layer of mud and hydrocarbon sludge. Heavier crudes and crudes containing high solids contents will cause a more rapid build-up of the mud layer. Mudwashing is the process by which this layer of sludge is removed from the vessel into the effluent brine for downstream treatment. There are a number of problems associated with the build-up of a layer of sludge at the bottom of the desalting vessel: The layer effectively takes up volume normally occupied by the aqueous phase, thus reducing the water residence time in the vessel. This leads to high oil-inbrine entrainment, high chemical additive rates and poor performance. Partial blockage of the effluent brine outlet lines can occur, resulting in poor flow patterns and vortexing in the vessel which increases the entrainment of oil into the brine. Removal of the sludge is accomplished by agitation of the layer by direct injection of higher pressure water or steam through a header system, typically 18 up from the vessel bottom. The agitation of the layer causes the solids to be suspended in the water, allowing them to be easily removed through the brine outlet lines. The header system may consist of a single line of water nozzles along the centre-line pointing directly downward, or a dual header with two lines of nozzles along either side of the vessel pointing down in parallel to the vessel walls. Inlet nozzles are spaced every 3 - 6 feet and are designed for a water flow of between 5 - 10 gallons per minute, with a pressure drop of 5 - 10 psi across them to ensure adequate agitation. It is recommended not to fall below the design wash water flow rates or the efficiency of mudwashing will fall dramatically. At adequate flow rates, mudwashing should be relatively rapid and it should never be necessary to mudwash for longer than ~30 BP Amoco Treatments Handbook
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minutes before observing a significant improvement in the effluent brine quality. Exact designs will vary depending on the manufacturer and the particular conditions. The mudwashing wash water may come from a number of sources: Recycled effluent brine - Recommended by Petreco (now Baker Petrolite). Effluent brine recycling maintains a constant effluent brine outlet flow and thus a constant level in the desalter during the mudwashing process. The most significant problem with this mode of operation is that the effluent brine will become very dirty during mudwashing and some plugging of the wash header nozzles is likely, leading to localised solids build-up and vortexing in the vessel. This may lead to significant oil carry-under during the process. Nonetheless, recycled effluent brine is the source of wash water recommended by BP because experience has shown it to give the most stable operation. Fresh wash water - Recommended by Axsia Howmar (formerly Howe Baker). The wash water is clean therefore does not worsen the problems of outlet line blockage, but the increase in water feed volume to the desalter may exceed the capacity of the outlet brine controller. This can lead to an increase in the water level in the vessel and subsequent downstream upsets. It is also very important not to use water intended for use as the desalter wash water. Desalter performance is critically dependent on the rate of wash water addition, and any reduction in feed rate can cause unacceptably poor desalting efficiency. Fresh mains water - The addition of mains water incurs the same problems as the addition of fresh wash water but is more expensive. It is therefore not recommended. Steam - Injection of steam at a pressure of at least 2.5 bar greater than the desalter pressure can lead to very effective mudwashing. However, steam injection can also be too turbulent, leading to level control upsets and operational disruptions. The frequency of mudwashing should generally be determined by the unit performance. Excessive oil levels in the effluent brine, excessive chemical addition rates and cold effluent brine lines are all signs that more frequent mudwashing is required. In general, there is no significant advantage to maximising the time between mudwashes unless the operational upsets caused during mudwashing are severe. For a desalting system running a crude with average solids content, a frequency of one wash per week, lasting up to 30 minutes each time, is typical, although on single stage desalters and the first stage of multi-stage desalters daily mudwashing is quite common. There are a number of common operational problems associated with mudwashing. The increase in water volume during the mudwashing operation can cause the water level to rise and the water level control valve will open to allow more effluent brine out. The crude feed rate to the unit is normally governed by the desalter pressure, so as the brine outlet valve opens, the crude feed rate to the unit increases to compensate. When the water level returns to normal, the water level control valve closes and the crude feed rate will be restricted to allow the water interface level to normalise. These control valves are often set to proportional control and react slowly to changes. As a result, the water-oil interface level oscillates and the crude feed rate varies. In fact, the BP Amoco Treatments Handbook
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crude feed rate to the unit can vary by as much as 5 - 7% in magnitude, resulting in preflash and atmospheric tower upsets. 20. Troubleshooting Figure 3.11 shows the recommended troubleshooting tree for desalter operation. Most of the easily remediable operational problems encountered in day-to-day running can be dealt with by following the recommendations contained within. Desalter operation is always a compromise between effective desalting of the crude and environmental difficulties arising from the treatment of high oil and solids content effluent brine. Many problems, such as those arising from running crude charge rates in excess of design or from running problem crudes, can only be minimised by optimising desalter efficiency within the imposed constraints. Further troubleshooting solutions to the likely problems encountered include: Maximising the temperature of operation where possible, to improve the efficiency of desalting overall. Optimisation of wash water addition rates by considering Section 3.3.4. Generally, small increases in water rate may yield improvements in salt and solids removal. Lowering the wash water pH to destabilise emulsions. Consider more frequent or continuous mudwashing. Blending of heavier crudes with lighter oils to improve desalting efficiency. Blends must be considered carefully because problems can occur. The blending of light, paraffinic crudes into heavy, asphaltenic crudes can cause precipitation of asphaltenes in the desalters. Oil conductivity may also increase upon blending, which may cause transformer trip-outs. Crude tank dewatering to remove as much salt and water as possible upstream. Optimisation of the chemical addition program in conjunction with the supplier. In particular, the addition of a wetting agent may yield very impressive results. Short bursts of high demulsifying agent addition rates may help control upsets for short periods of time. Vary the chemical addition point. Consider injection of demulsifier into the crude tanks, thus increasing residence time and improving the efficiency of tank dewatering. Vary the mixing pressure drop to help destabilise the emulsion or improve the rate of solids removal Analyse the wash water and crude oil to pinpoint possible problem causes. Consider changing the wash water source or improving the wash water quality. Consider the addition of effluent brine deoilers (recycling the oil recovered) to improve the quality of the brine and to allow optimisation of the oil dehydration at the expense of oil carry-under. Improve level control using more accurate probes. Better operator training and awareness. BP Amoco Treatments Handbook
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As a last resort, if desalter operation is unacceptable despite all attempts to optimise, it may be that the existing design is simply inadequate for the required duty. In that case, significant capital expenditure will be necessary. Internal modifications may be sufficient, such as switching to more efficient electrical grid designs or higher duty transformers. Finally, vessels may need to be replaced with larger designs or the addition of further desalting stages may be necessary.
3.6
Wash Water Sources
Ideally the wash water used in the desalting vessels should be clean, fresh process water. However, use of fresh water may not always be practical or economic because it will significantly increase the load on the effluent water treatment unit and may be in short supply. As a result, used process water is normally used, from sources such as sour water stripper bottoms, vacuum condensate and tower overhead waters. 21. Impurities The key impurities in the wash water are ammonia, sulphides and phenols. Wash water pH is also a major concern. The disadvantages of each impurity are as follows: Ammonia - If the desalter pH is greater than 7, ammonia may pass unaffected through the desalters and react with HCl in the crude oil forming chloride salts, which deposit in the CDU overheads. CDU towers have been found to be completely salted up on the top few trays and the top pump-around as a result of high ammonia levels in the feed. Ammonia may also react with naphthenic acids forming stable emulsions. Acceptable ammonia concentrations in the wash water are 30 - 40 ppm. Phenols - Phenols are preferentially soluble in the crude oil phase and so will be extracted from the wash water into the crude. This is advantageous because otherwise removal of phenols from waste water is very difficult. The phenols will tend to end up in the kerosene fraction downstream of the CDU where they may cause problems meeting colour and WSIM specs. Phenol levels of 100 - 200 ppm are acceptable. Sulphides - Sulphides may exist as insoluble sodium and iron salts, or as free H2S. The H2S will be absorbed into the crude oil in the desalter and end up in the CDU overheads where it contributes to acid corrosion and reacts with iron, forming more solid salts. The insoluble salts contribute to rag-layer stabilisation in the desalting vessel and can cause problems in the waste water treatment plant. Sulphide levels of 10 - 20 ppm are acceptable. Others - Other contaminants include Oxygen (dissolved) - increases the rate of corrosion in the desalter. Should be maintained below 0.02 ppm. Solids - encourage rag-layer stabilisation Sodium - from caustic use in the sour water strippers, or from caustic addition (see section 5.1). BP Amoco Treatments Handbook
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Hydrocarbons - vacuum tower condensate can contain high levels of slop oil which make the estimation of wash water feed rate inaccurate. 22. pH Control It is important to control the pH of the desalter wash water between 6.0 and 8.0. Above a pH of 8.0 emulsion-forming surfactants are produced by the neutralisation of organic acids, especially in highly naphthenic crudes. Below a pH of 6.0 emulsion-forming surfactants are produced by the neutralisation of amines. Swings in wash water pH are often responsible for upsets in desalter operation. The wash water pH should normally be controlled by the injection of an acid, such as H2SO4, if required. Injection of the acid into the wash water stream just before mixing with the crude is preferable, but may be done at the sour water stripper or other water source. Careful selection of materials is required to prevent local corrosion, and the injection system should be designed to ensure good mixing of the acid into the water stream. The effluent brine pH must be controlled above 5.5, preferably continuously, or excess H2SO4 may break through to the CDU causing deposition of sulphate and sulphite salts. 23. Sour Water Stripper (SWS) Bottoms A typical SWS feed can contain up to 6000 ppm sulphides, 7500 ppm NH3 and 1000 ppm phenols (particularly FCC sour water). BP Amoco Oils current guidelines for stripped sour water specify levels of 1 - 5 ppm H2S and 10 - 50 ppm NH3. High ammonia content can cause desalter upsets and overhead salt deposits (of NH4Cl) in the CDU. Caustic is normally added to the stripper to increase the stripping of NH3. As a result, the stripped sour water is basic with pH 8.5 - 9.5, and pH correction will normally be required before injection into the crude as wash water. SWS water may also contain significant levels of ammonium polysulphide ((NH4)2SX) which is used to prevent cyanide corrosion in the stripper. Unfortunately, when the pH falls below 7.5 the polysulphide decomposes giving elemental sulphur which will deposit causing blockages and corrosion. Care must therefore be taken when using SWS water to optimise the conditions of injection under given circumstances. Amines should be kept out of the SWS by recycling amine unit blow-down streams, and reducing the amine unit carry-over. 24. Vacuum Condensate Vacuum condensate can contain high levels of slop oil hydrocarbons. This hydrocarbon can take up a significant volume fraction of the total flow, thus reducing the actual wash water flow to the desalters. Account must therefore be taken of the hydrocarbon content. High hydrocarbon contents can also indicate the presence of cracked components from the vacuum gas oil which can be excellent emulsion stabilisers. 25. Other Sources
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There are a number of other sources of wash water which may prove acceptable under certain circumstances but are, in general, likely to cause extensive operational problems. Steam blowdown and cooling tower water are likely to contain high levels of solids and other impurities; sour coker water will contain high levels of coke fines and unstripped fractionation tower overheads are likely to contain impurities at levels too high to prove acceptable for good desalter operation. Water containing phenols should be sent to the desalter, since the phenols are extracted by the crude and end up in product streams.
3.7
Chemical Additives
The problems associated with the high content of natural surfactants in crude oil, such as filterable solids, asphaltenes and waxes, mean that effective desalting is generally only possible by the application of a well-designed chemical additive program to help break down emulsions and remove solids from the crude. The capital costs associated with additive injection are low and the operating costs are small compared to the operational benefits. Chemical additive manufacturers will normally recommend an appropriate solution package and in many cases will operate the chemical additive program on site for the refinery. The technical expertise of the supplier enables them to select the most appropriate additives required. However, it is important to have a solid understanding of the basic principles behind the function of these additives and the effects of operational variations. There is a separate section in the Olympus Treatments Handbook, Chemical Additives - Process Side on Emulsion Breakers (Demulsifiers) which provides a more detailed description of the chemistry involved. Even more details on demulsifiers and emulsion polymers are given by Micheal Dion of Betz (now BetzDeraborn) presented a paper in 1995 on Desalting Opportunity Crudes. 26. Demulsifiers Demulsifiers are essentially surface-active agents whose main effect is to lower the surface tension between two-phases at a surface, thus improving the rate of droplet coalescence. There are a wide variety of commercially available demulsifiers and the suitability of each to a particular water-oil emulsion depends sensitively on the exact conditions, such as oil type, solids content, salt content etc. Past experience and careful analysis will enable the chemical supplier to make the most appropriate choice. The emulsions found inside desalter vessels are water-in-oil emulsions: the crude oil is the continuous phase. It is therefore most effective to use a demulsifier which is injected into the oil phase and migrates to the oil-water interface through the crude oil. Most demulsifiers are large, oil-soluble organic compounds, often alkyl-substituted - + benzene sulphonic acids (R--SO2O M ), alkyl phenolic resins (-(R)-), or substituted polyalcohols (-((CH2)xCH(OH))-). These compounds can provide effective emulsion breaking in very small doses. Sometimes combinations of compounds are required to suit the particular emulsion formed.
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Injection of the demulsifiers is best carried out as far upstream as possible of the desalters in order to increase the residence time of the demulsifying agent in the crude to give it more time to diffuse to the oil-water interface. In extreme cases it may be necessary to inject the demulsifier into the crude storage tanks to maximise residence time, with tank dewatering carried out before the crude is drawn. On multi-stage desalter systems, splitting the demulsifier injection so that some is injected before the second stage vessel may be beneficial. Injecting oil-based demulsifiers into the wash water stream (to decrease the distance molecules have to travel to reach the interface) is unlikely to yield improved operation. The optimisation of demulsifier addition is best carried out empirically by varying the rate until the best compromise between cost and operation is reached. Typical injection rates give demulsifier concentrations of 3 - 12 ppm in the crude. 27. Wetting Agents Filterable solids tend to accumulate at the oil-water interface where they stabilise emulsions. These solids are almost entirely coated with oil molecules and are hard to remove from the oil phase. It is preferable, however, to remove them from the crude into the effluent brine in the desalter vessels to prevent them from causing problems downstream. Water washing alone will not achieve very good removal efficiencies. Wetting agents are compounds with a functional group at one end strongly attracted to the solid surfaces and a group at the other end strongly attracted to water. These agents are normally water-based and diffuse through the water until they meet a solid particle, whereupon they attach themselves to it, displacing the surrounding oil molecules, and drag it into the aqueous phase. Some wetting agents are polymer-based. Care should be taken when adding these to high solids crude oil runs because in high doses they can agglomerate around the solids, forming large solid masses which cause extensive damage to the desalter internals. The dosage rate should not exceed the recommended maximum, typically 0.5 - 2 ppm on crude. Wetting agents are very effective at increasing the removal of filterable solids from the crude. In doing so they help prevent the formation of large rag layers and destabilise emulsions. Refineries finding high solids levels in downstream operations, particularly high iron levels, should consider an improved program of wetting agent injection at the desalter. 28. Reverse Breakers These are demulsifying agents which are added to the wash water before injection into the crude (see the above-mentioned article by Dion), whose main purpose is to reduce the amount of oil carried under into the waste water treatment system. These agents are normally long chain polymers with molecular weights in excess of 1 million, such as the Novus polymers from Betz. The concentration of oil in the effluent brine can be reduced from 10% - 15% to just 500 ppm. Additional benefits include: The amount of primary demulsifying agent required for efficient desalting may be reduced by 10% - 60% with possible overall chemical additive cost savings of up to 50% BP Amoco Treatments Handbook
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A reduction in the size of the interface rag layer, leading to increased salt and solids removal, longer oil residence time and better electrical performance resulting from the thinner interface layer Increased operational flexibility and the ability to drive the desalting system harder
29. Other Variables A number of other variables should be considered: pH - natural surfactants in the crude oil are more stable at higher pH values, above 8.5. Desalter operations should be maintained, where possible, below pH 8 depending on the crude, wash water quality and pH requirements of the additive program. Temperature - Higher temperatures help remove the natural surfactants from the oil-water interface and increase the mobility of the chemical additives through the oil phase. Oil in Brine - Water-wetted solids will still be coated with small amounts of oil which end up in the effluent brine. However, because of the reduced amount of oil in the coatings, the actual amount of oil entrained into the effluent brine will be reduced despite the increased removal of solids.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Consequences of Impurities
4.
4.1
Consequences of Impurities
Corrosion
The presence of soluble inorganic chloride salts in the crude is the main contributor to corrosion problems in downstream units. In particular, chlorides cause major corrosion problems in the CDU overheads. Chlorides are present as NaCl and as the alkali-earth metal salts MgCl2 and CaCl2, in typical molar ratios of 75:15:10. At the high temperatures found in the crude unit preheat furnace and the tower itself, the alkali-earth metal chlorides undergo a hydrolysis reaction in the presence of water to form HCl. NaCl is stable to hydrolysis under normal operating temperatures but may undergo localised hydrolysis in areas of high temperature such as the furnace tube walls. Hydrolysis Reaction MgCl2 + 2H2O Mg(OH)2 + 2HCl CaCl2 + 2H2O Ca(OH)2 + 2HCl NaCl + H2O HCl Minimum Temperature Required >250 F (121 C) >400 - 450 F (204 - 232 C) >1000 F (540 C)
The hydroxide salt products of these reactions are stable at the temperatures encountered in the crude tower and leave the CDU mainly in the bottoms product, finding their way into downstream residue processing units. The HCl gas formed in the reaction is not, in itself, particularly corrosive until it mixes with water, whereupon it forms hydrochloric acid which is extremely corrosive. The HCl, being a gas, concentrates in the CDU overhead (and to a lesser extent in the top pumparound) where it meets all the water vapour contained in the crude oil feed and forms hydrochloric acid. The acid then reacts with iron via the following reactions 2HCl + Fe H2 + FeCl2 FeCl2 + H2S FeS + 2HCl 2HCl + Fe H2 + FeCl2 2HCl + 2Fe + H2S 2H2 + FeCl2 + FeS When the salt products from the acid reactions precipitate out on the overhead condenser tube walls and overhead accumulator vessel walls, further corrosion problems can occur due to under-deposit corrosion. It is desirable to control the desalting operation such that the level of chlorides in the overhead water does not exceed 15-20 ppm. As a rule of thumb, 1 pound per BP Amoco Treatments Handbook
thousand barrels of salt in the desalted crude oil feed to the CDU can lead to ~42 ppm chlorides in the CDU overhead system. If the level of chlorides in the overhead system rises above ~30 ppm, unacceptable corrosion rates can result. Figure 4.1 - Crude Unit Corrosion
HCl Acid Corrosion

HCl H2O Kero
(Phenols)
Desalter
Crude Brine to Treatment
NaCl Mg(OH) 2 Ca(OH) 2
Sour Water Overhead Products Atmospheric Residue
Preheat Furnace MgCl2 + 2H2O --> 2HCl CaCl2 + 2H2O --> 2HCl
If desalter operation appears to be normal but the overhead pH is low, or the chloride level is still high, a possible cause may be a change in the ratio of Ca/Mg to Na salts in the crude: higher Ca/Mg levels will lead to significantly higher levels of overhead chlorides. Organic chlorides can be another source of chlorides in the CDU overheads. These pass unaffected through the desalter and can decompose in the preheat furnace to form HCl. Organic chlorides can be introduced into the crude at the oilfield to remove waxy deposits, or through the recycling of slops to the crude tower. Other organic halides can also contribute to the measured level of chlorides.
4.2
Fouling
Hardness salts such as calcium and magnesium carbonates and sulphates present in the desalted crude present different problems. These salts are insoluble in the oil phase. When the water evaporates in the preheat furnace, they deposit out on the side walls causing fouling in the heater tubes. This leads to greater maintenance costs and operational problems. As the temperature rises, these salts become less soluble in water and begin to precipitate out even if the water is not fully vaporised. They can also cause fouling in the preheat exchanger equipment, which reduces the rate of heat transfer and thus increases fuel costs or reduces the possible charge rate.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Consequences of Impurities Control of fouling may be effected in three ways: Prevent the formation of solids, Prevent solids adhering to heat transfer surfaces, Remove solids from heat transfer surfaces.
Adding part of the desalter wash water at the charge pump helps to keep salts in the crude in solution and reduce fouling in the cold pre-heat exchangers upstream of the desalter. However, adding the water to the pump suction, in order to use the pump as a mixer, should be avoided, because there is no control over the degree of mixing and a stable emulsion, which is difficult to separate in the desalter can result in worse fouling downstream. The formation of solids in the hot pre-heat exchangers and furnace downstream of the desalter can be prevented up to a point by efficient desalting (see section 3) and by not adding caustic (see section 5). However, there is a limit to which desalting can reduce solids, determined by the design of the desalter and the amount of oil permitted in the brine effluent. Keeping heat transfer surface temperatures to a minimum helps to keep fouling rates low. This can be achieved by ensuring high tube velocities, which will also help to prevent solids adhering to the surfaces. Fouling is often the result of low feed flows, or low flows resulting from the reconfiguring of heat exchanger trains with parallel flows in an effort to maximise heat recovery from low temperature streams. Tube inserts, which promote turbulent flow under viscous or low flow conditions, can help to prevent solid deposition and thereby reduces fouling, as well maintain high heat transfer rates due to the turbulent flow. Sometimes insoluble asphaltenes and solid particles form what is known as a rag layer at the oil-water interface in the desalter. If this is allowed to accumulate, it is periodically disturbed into the desalted crude and can result in high fouling downstream. This can be prevented by injecting a dispersant directly into the rag layer. Fouling of heat transfer equipment can result in very expensive maintenance. It is therefore worthwhile installing accurate online instrumentation to measure flows, temperatures and pressure drops across all the hot pre-heat exchangers, in order to monitor the effects of fouling over long periods.
4.3
Basic Sediments and Filterable Solids
Basic sediments and filterable solids will also contribute to the extent of fouling build-up in the crude preheat exchangers and, if not removed in the desalting vessels, will cause higher ash and sediment levels in downstream units, increasing the level of fouling there. A basic sediment level of 0.05% in the desalted crude equates to 300 cubic feet per day for a 100MBPD refinery. The problems caused by high levels of solids in the desalted crude are: Fouling of preheat exchangers - This can reduce the crude throughput, increase the fuel costs and reduce distillation efficiency leading to lower product yields and increased maintenance costs. BP Amoco Treatments Handbook
Tray plugging and foaming in the CDU - This results in decreased capacity and low distillation efficiencies and product yields. Particularly caused by filterable solids. Off-Spec products - The solids tend to concentrate in the residual fuels and can lead to products failing to meet ash content specifications. Erosion - Physical erosion of control valves, pumps, etc. due to impact with solids can be an important cost. Rag layer stabilisation - Filterable solids often cause rag layer growth and subsequent degradation in desalter performance. Distillate fuels - When burning distillate fuels, filterable solids can cause fouling and corrosion if they are entrained in the fuel.
Sludge in crude oil in storage tanks can settle to the bottom of the tank while allowing water to settle out. Some of the solids may be removed with the water, but not all of it. After draining off the water the tank contents should be well mixed for several hours in order to disperse any sludge and homogenise the crude before feeding to the CDU. This will help to avoid high concentrations of dislodged sludge, which can lead to the above problems.
4.4
Sodium in Residual Products
As shown in Figure 4.1, all the sodium salts entering the crude tower end up in the atmospheric residue stream leaving the CDU. The sodium will be 2 - 6 times more concentrated in the residual stream than in the crude feed. Problems caused by high sodium levels include: Catalyst Poisoning - Increased use of FCC catalyst, reduced lifetime of hydrotreating catalysts. Off-Spec Products - Many products have an upper limit on allowable sodium levels. Corrosion and Fouling - When burning fuels containing sodium salts corrosion and fouling can be a problem. Heater tube coking - High sodium levels harden the cokes formed on heater tubes, making them harder to remove. These problems can be prevented by efficient desalting, and by not adding caustic to control the overhead corrosion, (see section 5).
4.5
Water
Once the desalter operation is optimised, it is unlikely that much can be done to further reduce the level of entrained water into the desalted crude. Reducing the water level below about 0.1 - 0.2 vol% would result in unacceptably high levels of oil in the effluent brine. Figure 4.2 - Solubility of Water in Crude Oil
1.0
Water Solubility - volume %
0.8
0.6
0.4
0.2
50 API 40 API 30 API 20 API 10 API 200 250 300 350 400 450 500
0 150
Temperature (F)
Residual water left in the desalted crude presents a number of operational problems: Reduced charge rate - 0.2% residual water equates to a 200 BPD reduction in crude capacity for a 100MBPD refinery Increased heating costs - Water has both a high specific heat and a high latent heat so that small amounts of water in the crude significantly increase the amount of heat required to heat it up and vaporise it. Vapour Loading - When water evaporates in the furnaces and CDU to form steam, the steam will occupy 6 - 8 times the volume of an equivalent mass of hydrocarbon, which will reduce the charge rate even further.
Efficient desalting is the only way to avoid these problems.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment Caustic Addition
5.
5.1
Caustic Addition
Addition to Desalting Vessels
Caustic may sometimes be added into the desalting vessel itself in order to neutralise any acids contained in the crude oil and thus prevent acid corrosion of the vessel and internals. The main source of acids in crude oils are naphthenic acids, and their concentration can vary significantly between crudes. Naphthenic crudes may have a pH as low as 3 - 3.5 in the desalter and acid corrosion can result. Caustic neutralises the naphthenic acids, forming sodium naphthenates. These have large hydrocarbon chains attached to an ionic, water-soluble end group and make ideal emulsifying agents. Above pH 7.5 the presence of naphthenates can result in the formation of highly tenacious emulsions in the desalting vessel, leading to severe operational difficulties. The use of caustic as a neutralising agent upstream of the desalting vessels is therefore not recommended. The problem of low pH effluent brine is best dealt with in the downstream water treatment plant and by appropriate metallurgy.
5.2
Addition Downstream of Desalters
The injection of caustic into the crude downstream of the desalting vessels is a method often used to help control CDU overhead corrosion rates. When chloride concentrations in the CDU overheads exceed the recommended limit and the desalter is already operating at optimum conditions, caustic injection may prove to be an effective way to reduce the level of chlorides. Caustic reacts with the salts responsible for the high overhead chloride level before they can hydrolyse in the preheat furnace to form HCl: MgCl2 + 2NaOH Mg(OH)2 + 2NaCl CaCl2 + 2NaOH Ca(OH)2 + 2NaCl HCl + NaOH NaCl + H2O FeCl3+ 3NaOH 3NaCl + Fe(OH)3 The sodium chloride formed is stable to hydrolysis at the temperatures commonly encountered in the system and so the level of chlorides (as HCl) in the overheads will fall. Caustic will also neutralise any other weak or strong acids present in the crude and so it is impossible to estimate the stoichiometric amount of caustic required. This means that it is very difficult to optimise the amount of caustic added.
5.3
Disadvantages of Caustic Addition
The disadvantages of adding excess caustic to the desalted crude are significant and can often outweigh the benefits: The hydroxide salt products of the reactions in Section 5.2 are insoluble in crude oil. The solids formed can cause big increases in pre-heat exchanger fouling and furnace tube coking, with significant associated costs. Unreacted caustic will rapidly increase the rate of fouling and vacuum furnace coking. Only 6 ppm of free caustic will increase the rate of coking by over 50% and by over 400% at 240 ppm (Mixed Arabian crude - Nalco). Free caustic can cause embrittlement and stress cracking in stainless steel and alloys at temperatures above 300F (150C). If the caustic is poorly mixed before entering the CDU preheat furnace, pure caustic deposits can form on the tube walls when the water evaporates, leading to under-deposit corrosion. Unreacted caustic entering the flash zone of the CDU or VDU can increase the extent of foaming, reducing the vapour-liquid separation rate and thus the fractionation efficiency. Maximum specified sodium levels in residual fuels are exceeded, causing fouling when burnt. This results in the need to use valuable cutter stock in these fuels to meet the specs. High caustic levels in the feed to a coker unit can cause increased coking in furnace tubes as a result of increased precipitation of asphaltenes. They also cause coke drum foaming, as well as off-spec product. The cost associated with this has been estimated between $25 - $100 per day per ppm of feed sodium increase for a 20 MBPD coker. The costs associated with off-spec product can be prohibitive if the desired product is anode-grade coke and the final product is unable to be sold as such. Sodium contributes to top bed fouling in fixed-bed reactors and can cause capacity limitations for units which are pressure-drop limited. NaCl can decompose on the surface of FCC catalysts at temperatures as low as 930F (500C), giving HCl which then contributes to salt accumulation problems in the FCC fractionator. Caustic inhibits the activity of many anti-foulant additives. Sodium is a catalyst poison for FCC, hydrotreating and reforming catalysts. High Na levels in FCC feed will significantly increase catalyst use rates. All fresh FCC catalysts contain a small quantity of residual sodium, depending on the manufacturing process. This is typically in the range 0.3 to 0.5 wt.% as sodium oxide, equivalent to 0.11 to 0.19 wt.% as sodium. It is the additive sodium from the feed which has the major impact on catalyst activity. When additive sodium deposits on the catalyst, it tends to neutralise acid sites and can cause pore collapse and zeolite encapsulation, both of which cause permanent activity loss. For modern catalysts, sodium can normally be tolerated on E-Cat up to about 0.8 wt.%. It is estimated that every 0.1 ppm incremental increase in FCC feed sodium above the steady-state value (typically 1.2 ppm) for a 50 BP Amoco Treatments Handbook
MBPD unit can cause an increase in catalyst addition rates of ~300 kg per day from 3.5 tonnes/day, in order to maintain catalyst sodium levels. This would cost about $550 per day. Costs will vary between $200 and $700 per day depending on the catalyst type (variable sodium tolerances) and the particular FCC mode of operation.
5.4
Caustic Injection Rate
The list of the disadvantages of caustic addition provides a substantial argument against its use to control overhead chloride levels. However, if the desalter operation is already optimised and other options are limited, the use of caustic addition can be economic. The problems are caused, in the main, by excess injection levels resulting in free caustic in the crude. These problems can be minimised by careful monitoring of the effect of caustic injection on the overhead chloride level. The relationship between caustic injection rates and overhead chloride concentrations is not linear. Experience shows that it takes 3 - 4 times more caustic to reduce the level from 50 ppm to 10 ppm than from 100 ppm to 50 ppm. This is because the HCl acid precursors can exist in forms which react poorly or slowly with caustic, for example as large crystals or as organic chlorides. As a result, caustic should not be used to attempt to lower overhead chloride levels below 10 ppm. Doing so would guarantee the presence of excess free caustic in the crude and exacerbate all the problems mentioned in the above section. The best procedure to adopt is to slowly increase the rate of caustic addition day-by-day while measuring the overhead chloride level. When the chloride level stops decreasing by a significant amount, or 10 ppm is reached, the caustic addition rate should be slightly decreased. This should ensure a good compromise between corrosion control in the CDU overheads and caustic-related costs downstream. Industry-wide caustic injection rates vary between 0.1 - 5 lb per 1000 bbls crude. The general consensus is that the lower the injection rate, the better. It is also better that the caustic be as dilute as possible (i.e. 3 ~10 Baume) to minimise the potential for strong caustic to exist undiluted.
5.5
Caustic Injection Method
The optimum caustic injection point depends on a compromise between maximising the degree of mixing between the caustic and the crude, minimising corrosion resulting from the presence of free caustic and minimising the fouling in the preheat exchangers and furnace tubes resulting from the precipitation of the inorganic salts formed in the neutralisation reactions. There is strong evidence both within BP Oil and industry-wide that injection of caustic into the crude immediately downstream of the desalting vessels and upstream of the pre-heat exchanger train will result in extensive fouling in those exchangers, the cost of which could be excessive. Injection of the caustic directly upstream of the crude preheat furnace is not desirable because much of the chloride precursors will already have hydrolysed to HCl. Further, when the water in the caustic BP Amoco Treatments Handbook
solution flashes off in the furnace tubes, pure NaOH will be left as solid crystals and these may accumulate at the tube walls and melt into liquid (dry NaOH melts at 604F (318C)). The HCl is a vapour at the furnace temperatures and flows mainly through the centre of the tubes. There is therefore less contact between the two phases than expected, despite the turbulent flow regime, and less neutralisation occurs than predicted by the stoichiometry. However, these disadvantages are outweighed by the problems of fouling in the preheat exchangers and so it is recommended to inject caustic just after the last preheat exchanger as far upstream of the CDU preheat furnace as possible to maximise contact time. The caustic injection system must be designed to maximise the degree of mixing between caustic and crude to make full use of the available caustic. It is preferable to inject the caustic into a slip stream of the desalted crude. This slip stream should contain an in-line mixer (either static mixer or mixing valve) to ensure that the caustic solution is well emulsified with the crude before re-entering the main stream. Injection into the CDU feed line downstream of the preheat furnace is not recommended. Most of the chloride precursors will already have hydrolysed, and flow in this line is less turbulent than in the furnace and good contact between phases is even less likely, so that the extent of neutralisation will be poor.
5.6
Spent Caustic
Injecting spent caustic into the desalted crude to control CDU overhead chloride levels is often seen as a convenient and inexpensive way to get rid of the spent caustic, in particular to prevent phenols, which are expensive to remove, from entering the waste water treatment system. The spent caustic normally comes from Merox units or H2Sremoving caustic washes. As a result, the caustic will likely contain high levels of sulphides, mercaptans, phenols, naphthenates, thiophenols and solids. The main disadvantages of adding spent caustic to the crude, other than those already mentioned in section 5.3, are: Spent caustic can vary widely in concentration, making it very hard to control the addition rate. Since it is often very dilute, higher injection rates may be required, increasing the water content of the crude. Mercaptans are recycled into the crude, increasing the sulphur levels and the load on downstream Merox units. Phenols and thiophenols are preferentially soluble in the crude oil phase and will accumulate in the jet fuel, leading to difficulties meeting colour and WSIM specs. The solids and other impurities, such as naphthenic acids, will contribute to rag layer and emulsion formation, and increase fouling rates. Ideally, spent caustic should not be used for corrosion control on crude units. However, the economics may sometimes show a cost benefit for disposing of the spent caustic in this way, and in that case it is desirable to store the caustic in a tank where its strength is adjusted to a constant, known value before injection into the crude. BP Amoco Treatments Handbook
5.7
Summary
The use of caustic for corrosion control of the CDU tower overheads is not recommended because the associated problems of increased fouling, coking of furnaces and catalyst poisoning normally outweigh the benefits. Corrosion control in the overheads should be carried out by a program of injection of neutralising agents and corrosion inhibitors directly into the overheads themselves. However, in certain circumstances, caustic injection may prove to be the most economical solution. In that case, a carefully applied program with conservative control can have a very good impact on the rate of overhead corrosion, with minimised disadvantages. Spent caustic may also be used as a convenient disposal method, but engineers should be aware of the possible problems which may result.
BP Amoco Treatments Handbook Section D - Crude Oil Treatment
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6.
6.1
CDU Overhead Corrosion Control

CDU Overhead Systems
The condensation of the overhead vapour from the Crude Distillation Unit (CDU) and the provision of reflux to the column can be effect in a number of ways, as shown in the following three figures. In the first, reflux is provided by cooling a liquid pump-around at the top of the column, so that only the product naphtha and aqueous phase are condensed. Figure 6.1 - CDU Overhead with Pump-around Reflux System
O/H LINE O/H CONDENSERS VAPOR WATER WASH CRUDE COLUMN TOP PUMPAROUND O/H ACCUMULATOR NAPHTHA
SOUR WATER
In figure 6.2, the reflux pump-around is replaced by a partial condenser and separate reflux drum. Only the heaviest vapour, which condenses above the water dew-point, is used as reflux. The remaining vapour is condensed and collected in the accumulator, which separated the water from the oil and non-condensables. Figure 6.3 shows the most common system in which the reflux and product streams are condensed together and collected in a combined accumulator / reflux drum. The accumulator acts as a three-phase separator. Uncondensed vapour is removed to control the column pressure, water is removed to control the interface level, and the oil phase is split between reflux which controls fractionation in the column, and product which governs the liquid level in the drum. BP Amoco Treatments Handbook
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Figure 6.2 - CDU Overhead with Separate Reflux Drum
O/H LINE O/H CONDENSERS VAPOR WATER WASH CRUDE COLUMN REFLUX DRUM O/H ACCUMULATOR NAPHTHA
SOUR WATER
Figure 6.3 - CDU Overhead with Combined Reflux Drum and Accumulator
O/H LINE O/H CONDENSERS WATER WASH VAPOR
CRUDE COLUMN
REFLUX DRUM / O/H ACCUMULATOR
NAPHTHA
SOUR WATER
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6.2
Causes of CDU Overhead Corrosion
Crude oils contains varying levels of water, salts and sulphur compounds. Some of the salts originate from the rock from which the oil was extracted and some from sea water contamination during transport by sea tanker. Sulphur compounds include both H2S and organic sulphur compounds, such as mercaptans, thiophenes, etc. These impurities, if not removed, are the precursors of potentially corrosive acid gases such as HCl and H2S. In addition, low molecular weight carboxylic acids (acetic, propionic, etc.) and sulphoxy compounds (sulphites, sulphates and thiosulphates) have also been found in crude overhead systems. The current tendency to process heavier crudes, with higher sulphur levels and which are more difficult to desalt because of their high SG and viscosity, is resulting in increasing problems of CDU overhead corrosion. Crude oil salt and water levels can be reduced by ensuring that the crude oil is thoroughly water drained in storage before it is fed to the CDU. Low crude temperatures and heavy viscous crudes require longer settling times and more careful draining than lighter crudes. Storage mixers, which are often run in order to blend the crude and reduce the build-up of sludge, should only be used after water has been properly drained from the tanks. Desalting (see section 3) the crude is performed to remove salts and some sediments from the crude by thorough mixing with water. The salts dissolve in the water and the resulting emulsion is separated by long residence time, chemical emulsion breakers and the effects of a strong electric field. Unfortunately, desalters are expected to provide both good mixing and good separation of the resulting emulsion, and this is not always achieved with maximum efficiency. Poor mixing can result in salt not being dissolved by the water. Poor separation can result in carry-over of water containing salts. 30. Hydrogen Chloride The bulk of the salts in crude oil are chlorides of sodium, magnesium and calcium, occurring roughly in the same proportions as their ratios in seawater: 75 / 15 / 10. At temperatures found in the crude unit preheat furnace and the CDU itself, MgCl2 and CaCl2 are hydrolysed in the presence of water to form HCl (see section 4.1). An efficiently run single stage desalter should achieve between 0.1 and 0.3 wt.% water in the crude, and between 1 and 30 ppm salts, depending upon the initial salt concentration. Unfortunately, because NaCl is more easily removed in the desalter, the proportion of MgCl2 and CaCl2 will be higher than in the original crude, leading to a higher formation of HCl than would otherwise have been expected. The HCl gas formed by the high temperatures of the furnace flow to the top of the CDU with the light overhead vapour. HCl gas is not, on its own, corrosive to mild steel. But as water begins to condense in the overheads, gaseous HCl dissolves to form hydrochloric acid. The first drops of condensate will dissolve HCl to the extent that the BP Amoco Treatments Handbook
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pH can be as low as 3.0, which is very corrosive to mild steel and brass, the materials commonly used in overhead condensers, as shown in the following chart. Figure 6.4 - Corrosion Rate of Carbon Steel as a Function of pH
1,200 1,000 Corrosion Rate (mils per year) 800 600 400 200 0 1 2 3 4 5 6 7 8 pH 9 10 11 12 13 14
Hydrochloric acid attacks the mild steel according to the equation: Fe + 2HCl ! FeCl2 + H2 When H2S is also present (see below) this reacts with the ferrous chloride, releasing more HCl, which is then able to attack more of the steel: FeCl2 + H2S ! 2HCl + FeS The resulting iron sulphide serves as a protective barrier for the carbon steel, assisting in retarding further corrosive attack. 31. Hydrogen Sulphide Sour crudes contain over 1.0 wt.% of sulphur. Some of this will be dissolved H2S, the remainder will be mostly organic sulphides, mercaptans, thiophenes, etc. some of which will decompose to produce more H2S in the furnace. The H2S gas also flows up the CDU column and overhead with the light vapours. H2S corrosion can occur in the absence of water, but only if the metal temperature exceeds 230 C. This dry corrosion is typically found in flash zones and furnaces processing sour crude slates. The temperatures in most crude overhead systems are too low for this type of corrosion. The degree of H2S aqueous corrosion depends primarily on the partial pressure of the H2S, the condensate pH and, to some extent, the HCl level. The mechanism is rather complex, again depending on these three conditions. HCl intervenes as shown in the above section, while the effect of pH is shown in the following chart. BP Amoco Treatments Handbook
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Figure 6.5 - Corrosion Rate and Iron Sulphide Formation as a Function of pH
CORROSION RATE
IRON SULFIDE
IRON BISULFIDE
LOW pH
POLYSULFIDE FILM
4 4.5
6 pH
6.8 7.3
The chart also shows how the corrosion products depend on pH. At low pH iron sulphide is formed, probably because the low pH is due to the presence of HCl, with the sulphide being formed as shown above. Above pH 6.5, water solubilities of salts and the stability of the protective iron sulphide film decrease leading to the conversion of iron sulphide to the bisulphide, Fe2S3. At even higher pH a polysulphide film is produced. The solubility of iron sulphide, as shown below, depends on both its concentration and the pH. Figure 6.6 - Solubility of Iron Sulphide as a Function of pH
Solubility of Iron Sulfide (FeS) ppm 10,000 1,000 + * 100 10 1 0.1 0.01 0.001 0.0001 4.0 4.5 5.0 100 ppm 200 ppm 5.5 pH 6.0
+ *
+ *
20 ppm 50 ppm + *
+ *
+ * + * 6.5 7.0
32. Organic Acids
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Low boiling carboxylic acids, such as acetic, propionic and butyric acids can be present in the overhead vapour in small concentrations. However, their effect on the pH of the condensate is much less than that of HCl, and measures taken to overcome corrosion by HCl will also take care of these acids. Some crudes contain sufficient quantities of heavier organic acids, generally naphthenic acids, to cause severe problems in those parts of the CDU where operating temperatures exceed 230 C. Thus, naphthenic acid attack often occurs in the same places as dry H2S attack, such as heater tubes and the bottom sections of the column. 33. Organic Chlorides Organic chlorides constitute a contaminant in crude oil, often resulting from the carryover of chlorinated solvents which are used in the oil fields. They can also be picked up by the crude during transportation in contaminated tanks or lines. Organic chlorides are not removed in the desalter. Some of them can decompose in the heater, forming HCl and causing erratic pH control and accelerated corrosion in the crude unit overhead system as well as in downstream units.
6.3
Corrosion Control Measures
Corrosion in the CDU overhead system occurs as the result of acid and H2S attack in aqueous conditions. A number of control measures are available, such as: Material selection Blending Desalting Caustic addition Overhead pH control Filming corrosion inhibitors Water washing The operator does not always have the flexibility to choose the all of these measures at any one time. For example, once built the materials of construction cannot usually be changed, except at great expense. Similarly, the possibility of blending problem crudes with non-problem crudes to reduce corrosion problems may not exist, or blending may not provide enough reduction of the problems. Desalting is discussed in section 3, and it is assumed here that the desalter performance has been maximised. After a brief description of the preferred materials of construction, the following sections deal with the remaining options, which generally attempt to control conditions in which corrosion is minimised, particularly with reference to pH. As shown in figures 6.4 and 6.5, corrosion rates are lowest at high pH. However above pH 6.5 bisulphide formation results in high corrosion, and at even higher values other problems arise. Consequently, the pH is controlled in the range of 5.0 to 6.5. 34. Materials of Construction
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Normally, the policy within BP Amoco is to use carbon steel and ensure that the column top is not subject to condensation, and that the overheads are protected by neutralising and filming inhibitors (see below). However, if there are reasons that this is not possible and condensation may occur then more corrosion resistant material is required. Monel alloy 400 cladding and trays have been the traditional choice for this situation, but although it is quite good in HCl, it is adversely affected by H2S. The preferred choice for an alloy therefore is one of the NiCr-Fe-Mo alloys, the precise one being selected on the basis of expected pH. If the pH is not too low (i.e. pH >2) then Incoloy alloy 25-6Mo (or similar alloy) would be suitable. If conditions are more severe (i.e. pH <2) then Inconel alloy 686 or Alloy 59 would be preferable. 35. Caustic Addition The addition of caustic downstream of the desalter to combat HCl formation is discussed in section 5. Although an effective means of reducing overhead corrosion in the CDU, its disadvantages tend to outweigh the benefits. If caustic is used, it should be thoroughly mixed into the crude, for example by injecting a dilute solution into a slipstream of desalted crude, prior to mixing into the main process stream. Limits on the quantities added should be set, based on what is necessary for neutralisation of downstream chloride (20-30 ppm in the overhead water). 36. Overhead pH Control If the use of caustic is rejected, then the only way of controlling HCl formation is by good desalting, to reduce chloride levels in the crude. This has led some refineries to install two- or even tree-stage desalters. But with heavy, problem crudes the overhead water chloride levels may still exceed the recommended range of 5-10 ppm. Historically, ammonia has been used by injecting it into the overhead vapour line. Unfortunately, ammonia is not as soluble in water as HCl gas at the temperature and vapour pressure conditions at the water dew point in the overhead system. Consequently, the initial low pH not only causes acidic corrosion, but also causes the dissolving of the filming amine (see below) which therefore no longer provides a barrier to corrosion. Another problem with ammonia injection is that the neutralisation product, ammonium chloride, can sublime before the dew point, which can cause blockages in condenser tubes and high pressure drops. The sublimation point of ammonium chloride is determined by its partial pressure, and can be calculated. As a guide, levels of 100 to 150 ppm chloride in the overheads has given problems. Some refineries using ammonia carry out intermittent water washes of the overhead condensers, even when chloride levels are in the 5-20 ppm range. The use of sour water stripper bottoms as desalter wash water can introduce small amounts of ammonia which will result in natural neutralisation. The problems of ammonia injection at high chloride levels can be overcome by using neutralising amines. This should be injected into the overhead line upstream of the water dew point, and have three important characteristics, viz.; BP Amoco Treatments Handbook
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If the amine hydrochloride salt forms upstream of the water dew point, it must be a liquid that can be either mechanically moved by the hydrocarbon stream, so that there is no build-up of deposits. Vendors currently claim that the amine hydrochloride is slightly corrosive above the water dew point and therefore design the amine such that the salt only forms at or near the dew point. The amine must readily dissolve in water at the water dew point , in order to neutralise hydrochloric acid and prevent low a pH of the condensate. The amine must not react significantly with hydrogen sulphide, otherwise it will be rapidly consumed in sour service and be unable to neutralise acids. Furthermore, fouling and under-deposit corrosion can occur if the amine reacts with H2S before the water dew point. No amine tested at Sunbury displays all three qualities. Amines commonly selected for use are alkyl amines, (e.g. methylamine, di- and tri-methylamine) and alkanolamines, (e.g. monoethanolamine - MEA, dimethylethanolamine - MDEA, methoxypropylamine MOPA, ethylene diamine - EDA). As mentioned, the amine neutralises HCl by forming the amine hydrochloride: R3N + HCl ! R3NH Cl
+ -
Similar reactions occur with other acids. Normally theses salts are insoluble in the oil phase and are removed with the water. Their formation in the absence of liquid water, however, leads to salt deposits and under-deposit corrosion. BetzDearborn and Nalco claim success in lowering overhead chloride levels by injecting amines into the hot pre-heat. BetzDearborn claim this should only be considered if the overhead chlorides exceed 100 ppm. To be successful, the amine hydrochloride salts must be thermally stable at flash zone temperatures, since they will end up in the crude column bottoms. On the other hand, injection into the reflux when processing sour crudes can cause serious fouling. A heavy loading of bisulphide salts can accumulate on the top trays causing plugging and under-deposit corrosion. 37. Filming Corrosion Inhibitors Filming inhibitors function by the chemisorption of their polar groups onto metal surfaces. Common polar groups can contain nitrogen, sulphur or oxygen atoms usually in a heterocyclic ring structure. The polar group interacts with the corrosion products at the surface of the metal. Without the inhibitor, the natural FeS scale contains gaps and is easily removed, exposing bare metal to the corrosive environment. The inhibitor makes this scale uniform and resistant to penetration by the aqueous corroding agents.
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N H2C H2C C H2 Pyrimidines C R N R' H2C
N C R N R' C H2 Imidazolines Polyamines R (NH.CH2.CH2)n NH2
In CDU overheads, filming chemicals used for corrosion inhibition almost exclusively refer to either imidazolines and pyrimidines (both of which are oil-soluble), or polyamines (which are water-soluble). Their mechanism of reaction is based on one end of the molecule being electron-rich, so that it clings to the inherently electrondeficient metal surfaces. The other end of the molecule contains a long non-polar organic chain that orients itself away from the metal surface. The organic chains from adjacent molecules attract each other (as well as hydrocarbon from the process stream) to form an organic film barrier. Since filming chemical adherence to metal is electrostatic in nature, it is not very tenacious and must be replaced on a continuous basis (i.e. continuous injection). Filming chemicals are typically selected based upon good solubility in the continuous liquid phase of the process to facilitate and ensure rapid deployment to metal surfaces. Oil soluble inhibitors should be used where the hydrocarbon phase dominates, but if large quantities of water are added (see Below) then water soluble inhibitors should be used. Products of the main chemical additive companies (BetzDearborn, Petrolite and Nalco) are normally used, and these are often formulated for the typical conditions. Filming inhibitors have high molecular weights and boiling points, and will follow the paths of other liquids present following their injection. Therefore, they must be independently injected into both stages of a two-stage overhead system such as that shown in figure 6.2. Ideally, they should be injected into the horizontal pipework about 15 to 20 pipe diameters ahead of the condensers. They should not be injected in concentrated form, but diluted in naphtha in order to ensure better dispersion. Because of their semi-polar nature, filming inhibitors can act as surfactants. They can migrate to the surface of water droplets, preventing them from coalescing and separating from the oil in the overhead accumulator. This emulsification tendency varies significantly between products. If jet fuel is being produced from the crude unit care should be taken to select a filming inhibitor with a low emulsification tendency. 38. Water Washing At the water dew point the concentration of chloride is significantly higher than that seen in the water which collects in the reflux drum or accumulator. This is because the first drop of water formed is virtually saturated with HCl, which has been reported to be as high as 2000 ppm. To avoid this localised high concentration a water wash should be injected via a quill upstream of the condenser. The quantity of water injected should be calculated so that 30% of it returns with the condensate, (the other 70% vaporises and leaves the accumulator in the vapour phase). The water is injected to BP Amoco Treatments Handbook
Rev: 0 Date: 28 Feb, 2000 Page: x
force the water dew point to occur at the point of injection and ensure immediate dilution of the chloride. The water may be recycled from the accumulator. If multiple condensers in parallel are used, the addition rates should be independently controlled to each condenser. Neutralising amines and water-soluble filming chemicals should be added to the water wash just before it is injected. If ammonia is used for neutralisation, a water wash helps to prevent ammonium chloride deposits. Higher rates of water washing can be used intermittently to clean plugged condenser tubes. 39. Overall Strategy General CDU overhead system corrosion control strategy takes advantage of the iron sulphide film formation. Further protection of the metal surfaces is achieved with the formation of an organic shield by the addition of filmer to the system, and with the neutralisation of acids once conditions allow the establishment of a liquid phase. The addition of supplemental water is used at the point of condensation to assist in acid dilution and prevention of salt deposition. The degree of neutralisation should aim to control the pH of the condensed water in the range 5.0 to 6.5. 40. Corrosion Monitoring Several methods of evaluating the effectiveness of corrosion control programs can be employed, for example: Water analysis - for pH, metals, chlorides and hardness. Hydrocarbon analysis - for residual inhibitor and metals. Corrosion rates, measured by: electrical resistance probe, weight loss coupons, linear polarisation probes. Non-destructive examination by ultrasonics (UT) or radiography (RT). Routine analysis of the condensate water must be undertaken in order to control overhead corrosion. Continuous pH monitor reliability is poor, and so manual readings are need to determine the amount of neutralising chemicals to be added. Analysis for those metals present in the overhead system will indicate whether those metals are being dissolved by acids. The measurement of chlorides can help to confirm when a corrosion event began, and how long it was sustained. The hardness of condensing water should be zero, but if any hardness is detected it will indicate a leak in the watercooled condensers. If the water is recycled as wash water, a cooling water leak can introduce dissolved oxygen which will accelerate corrosion, and the hardness will precipitate when injected into the overhead line causing severe fouling. Sometimes it is possible to run a residual test on the hydrocarbon stream to determine the presence of the filming corrosion inhibitor. To maintain the film, there should normally be a residual of 3-5 ppm; anything higher would indicate a problem. The measurement of metals in the oil will rise when naphthenic crudes are process, but the BP Amoco Treatments Handbook
Rev: 0 Date: 28 Feb, 2000 Page: xi
ratio of iron to nickel (which corrodes very little) can be used to determine how much of the iron comes from the crude, and how much from corrosion. Electrical resistance probes can be inserted at most points in the overhead system and over a period of time will give an indication of the rate of corrosion of the probe. They can be read on-stream, and can be designed to be retracted through a packed gland and replaced on-stream. Weight-loss coupons yield a calculated corrosion rate based on the initial surface area and weight, but must removed in order to be inspected. Linear polarisation probes give an instantaneous corrosion rate based on the probe element corrosion current, but will only work in a conductive medium. They are useful in bulk water systems, and can be made retractable through a packed gland and replaced on-stream. Non-destructive testing is costly, and therefore used primarily as an inspection tool.
6.4
Overhead Accumulator Design
The overhead accumulator is a three-phase separator and should be designed in accordance with fundamental guidelines with respect to sizing and internals configuration. Its purpose is to collect and separate the naphtha and water phases, and to disengage the vapour. Liquid residence time is typically designed at 20 minutes, although in practice with well controlled columns, values as low as 5 minutes have been found acceptable. If there are auxiliary feeds to the accumulator, these should be added to a common header between the condensers and the accumulator. They should not be added directly to the accumulator vessel, since this could upset the oil-water interface. Naphtha leaving the accumulator should be free of acids, salts and emulsified water, all of which can contribute to increased corrosion in the column from the reflux, not to mention unacceptable levels of water in the product. The naphtha draw should be taken from a point where water has fully separated out, but which is always flooded to ensure the availability of reflux flow. Water leaving the accumulator should contain all neutralised acid salts. This is a critical part of the overhead system as it is the only route by which potentially corrosive salts can leave the oil circuit. Part of the water is recycled back into the overhead system as a supplemental water wash.
6.5
Further Information
Corrosion Control In CDU Overhead Systems: Guidelines A report sponsored and issued in 1995 by BP Oil, Sunbury. Dewpoint Calculation Sheet - General This spreadsheet will calculate the water dewpoint in a process under a given set of process conditions. The spreadsheet requires the input of process flow rates, pressure, BP Amoco Treatments Handbook
Rev: 0 Date: 28 Feb, 2000 Page: xii
temperature, and water profile. Water dewpoint is calculated based upon the relationship of temperature to the vapour saturation pressure of water. Calculations are valid for process temperatures and dewpoints from -160 to 700 F (approximately 100 to 370 C). Dewpoint Calculation Sheet - Crude Overhead Systems This spreadsheet will calculate the water dewpoint in an Atmospheric Crude Column under a given set of process conditions. The spreadsheet requires the input of process flow rates, pressure, temperature, water profile, and naphtha molecular weight and density. Total overhead flowrate is calculated based upon the sum of the Overhead Accumulator naphtha, water, and vapour effluent streams. Water dewpoint is calculated based upon the relationship of temperature to the vapour saturation pressure of water. Calculations are valid for process temperatures and dewpoints from -160 to 700 F (-100 to 370 C). Moisture Profile and Conversion Calculations This is an Excel spreadsheet which calculates the moisture profile of a gaseous process stream containing water vapour. It also calculates a new moisture profile for a change of temperature and pressure, and the rate of water condensation if the change in conditions results in condensation. Physical Properties of Neutralising Chemicals Provides details of amines used as neutralisers, and their hydrochloride salts, with some information on proprietary products. Physical Properties of Filming Chemicals Provides information on proprietary amines-based neutralisers. Three-Phase Separator Design This article on separators defines the layout and dimensions of separators generally. The sections on three-phase horizontal separators link to an Excel work-book, which contains three spread-sheets for the design of three types of horizontal, three-phase separator: with no boot nor weir, with a heavy-liquid boot, with a weir. A fourth sheet gives a table of recommended hold-up times. Use this spread-sheet to design or check the operation of a CDU overhead accumulator. Vendor & Product Listing Select Miscellaneous Equipment and choose a desalter vendor in order to access the vendor details and web-site

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BP Amoco Treatments Handbook Section D - Crude Oil Treatment Introduction

Rev: 0 Date: 28 Feb, 2000 Page: 1.1

Tel: 44-(0)1932 763400 Fax: 44-(0)1932 762985 Email: sanderrh@bp.com

Crude Oil Processing

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Introduction

Rev: 0 Date: 28 Feb, 2000 Page: 1.2

Cold Preheat Exchangers

Hot Preheat Exchangers

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils

Rev: 0 Date: 28 Feb, 2000 Page: 2.1

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils

Rev: 0 Date: 28 Feb, 2000 Page: 2.2

= 1.11 ISettle + 153.9 IAsph - 8.6 XSCl - 51.6 XSCa - 412

BP Amoco Treatments Handbook

Rev: 0 Date: 28 Feb, 2000 Page: 2.3

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils

Rev: 0 Date: 28 Feb, 2000 Page: 2.4

Figure 2.1 - Variation of Crude Oil Viscosity with Temperature

36 API 30 API 22 API 16 API

0.01 70 120 170 220 270 320

Relative Settling Velocity 30 API Crude

8000 7000 6000 5000 4000 3000 2000 1000 0

250 Temperature (F)

Relative Settling Velocity 16 API Crude

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils

Rev: 0 Date: 28 Feb, 2000 Page: 2.5

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Crude Oils

Rev: 0 Date: 28 Feb, 2000 Page: 2.6

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters

Rev: 0 Date: 28 Feb, 2000 Page: 3.1

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters

Rev: 0 Date: 28 Feb, 2000 Page: 3.2

Brine Effluent to Treatment

BP Amoco Treatments Handbook

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Desalted Crude to CDU

First Stage Desalter

Second Stage Desalter

Second Stage Brine to First Stage

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters

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Relative Settling Velocity

0.95 0.90 0.85 0.80

Relative Droplet Diameter

BP Amoco Treatments Handbook

Rev: 0 Date: 28 Feb, 2000 Page: 3.5

Figure 3.4 - Influence of Wash Water Addition on Coalescing Force

Relative Coalescing Force

Wash Water Addition Rate (Vol%)

BP Amoco Treatments Handbook

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters

Rev: 0 Date: 28 Feb, 2000 Page: 3.6

Emax C where Emax C d

Crude gravity - API 12 15 20 25 30 35 40

Temperature - F 300 290 270 260 250 240 230

Oil flow - BPD/ft2 20 50 100 150 175 200 250

Power - kVA/ft2 0.6 0.5 0.3 0.3 0.2 0.1 0.1

BP Amoco Treatments Handbook Section D - Crude Oil Treatment Desalters