The effective way of separating water from oil and oil from water

Clariant GmbH Division FUN Clariant Oil Services R&D 65926 Frankfurt am Main Germany

How it was in the early days

"Oil recovery in the early days" (Agricola,1556).

Nature took millions of years to convert organic sedimentation into liquid hydrocarbons, a process that is still continuing today. While mineral oilbased products have been used to some extent through the ages for many purposes, only since the last century have naturally occurring hydrocarbons become the world's principal source of energy. Petroleum is also a valuable and ever more important raw material for the chemical industry. But at our current rate of consumption, we have just 50 years of known oil reserves left. To counter this rate of depletion, new recources must be discovered and developed, an effort that is becoming more and more difficult and costly.

In its exploration for additional sources of hydrocarbons, the oil industry is therefore taking novel approaches to produce as much as possible from existing reservoirs. Here valuable assistance is provided by the chemical industry with compounds that enhance oilfield processes. Both industries have been partners since the very dawn of oil production. In those days salt water produced with the oil was virtually the death of an oil well, as there were no efficient means of separating emulsified water from the crude oil. Wet crude oil was stored in open earthen settling pits, warmed by steam or even just the sun and" dry crude" was skimmed off. However, this time-consuming method was unsatisfactory and disposing of the emulsions was becoming a real problem. Early in this century the first attempts were then made to use chemicals for breaking oilfield emulsions. Several hundred quarts of chemical per thousand barrels of oil (qtb) were initially required, and emulsion breaking and water separation were still slow and incomplete. Yet it was this innovation that marked the beginning of the ever more vital synergistic relationship between the oil industry and the chemical industry, neither of which could exist as we know it today without the other.

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And how it is today

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Flow chart of a modern wet crude oil dehydration and desalting system.

Numerous types of treating plants and processes are now used in the dehydration of wet crude oil that -together with time, heat, chemicals and sometimes an electrical field enhance the effect of natural gravitational forces. These techniques involve the separation of associated gas, solids and water. The separation of gas from crude oil in oilfield equipment, generally a minor problem, takes place before and during the oil dehydration stage. The major source of difficulty in oilfield operations is the removal of water and associated solids. Water is contained in most of the world's crude oils in varying proportions. Not only does this formation water form emulsions with the oil, but it may also contain salts to super-saturation level, as well as corrosive compounds such as hydrogen sulfide and carbon dioxide, and such solids as formation fines and corrosion products

View into a tankfarm for crude oil dehydration and storage.

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Sunrise over the oilfield.

Apparently in disorder, however a well engineered network of pipes, valves and pumps.

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The dehydration process

Produced natural emulsion of heavy crude oil and water, close up.

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 Emulsion breaking Coagulation Forced coalescence Gravity separation are the keys to a dynamic dehydration process

Temperature/viscosity behavior of a dry crude oil and the emulsion with 28ho v/v salt water content. Time for separation of water from a well-treated crude depends on the viscosity of the oil. The curve below gives an approximation of the settling time needed.

Not all impurities can be eliminated in the oilfield, but some must be controlled there before the crude is shipped out. Accordingly, refiners specify tolerance levels of oleophobic impurities such as water content, salts and solids. Such specifications help reduce transportation costs, render the oil suitable for refining and avoid costly corrosion damage to pipelines and distillation units. To comply with shipping limits, the basic oilfield treatment is centered on degassing, dehydration and solids removal. These processes require chemicals for emulsion breaking, dehydration and desalting corrosion inhibition scale prevention microbial activity control paraffin inhibition water disposal. Water content in crude oil varies from minute amounts to more than 90% vlv. Some water readily separates out and is referred to as "freewater". The rest usually exists in the form of a water-in-oil (wlo) emulsion, in which water is distributed as droplets in the continuous oil phase. Water and oil are immiscible liquids. Production operations introduce shearing forces which cause micro fine dispersion of one liquid in the other. In the presence of natural emulsifiers that are soluble, dispersible or wettable with oil or water -thus preventing separation of the two immiscible phases -stable emulsions are created.

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Untreated crude oil emulsion.

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Coagulation and early coalescence after the application of a Dissolvan demusifier.

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Dehydrated crude oil. The water has been separated almost completely.

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Depending on oilfield conditions, any of the following emulsion types may be formed : the regular or "classical" emulsion as the waterin-oil (w/o) type the reverse emulsion as the oil-in-water (o/w)

Effect of temperature and water content on emulsion viscosity. Approximate drop let size distribution before and after destabilization with demulsifier.

type
the multiple emulsion as the emulsionwithinan-emulsion, i.e. o/w within a w/o type.

The latter form is likely to occur when steam flooding is used to recover heavy crude oils. The natural emulsifiers are chiefly asphaltenes, oil resins, naphthenic acids, paraffins and waxes; inorganic materials such as clay, carbonates, silica, metallic salts, etc. can also act as emulsifiers. These compounds are adsorbed at the water-oil interface, forming a stable film and thus preventing the natural agglomeration and coalescence of the microfine dispersed water dioplets. Additional factors affecting the stability of oilfield emulsion are temperature, vicosity, water content and drop let size, gravity difference between oil and water, and age of the emulsion.

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Emulsion breakers: Their chemical structure and how they work

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Water separation curves are one of many measures to select the optimum demulsifier blend. An individual salt crystal in crude oil, close up.

Economical separation of crude oil from the produced water requires a combination of retention time, thermal and sometimes electrical treatment, and a correctly selected emulsion breaker. The action of these emulsion breakers, also called demulsifiers, being strong surface active agents, is to wet, disperse and displace the natural emulsifier film binding the oil/water interface, which then permits agglomeration, coalescence and gravity settling of the water droplets.

The Clariant range of Dissolvan demulsifiers consists of the following groups of surface active agents (surfactants): propylene oxidelethylene oxide (POIEO) blockpolymers crosslinked POIEO blockpolymers alkylphenol resins polyesteramines crosslinked phenol res ins cationic polymers finis hing products blended bases. All these compounds are ethoxylated and/or propoxylated to varying degrees to balance hydrophilic-oleophilic properties, solubility and dispersibility. They are specially tailored to act where they are required -at the oil/water interface. Their high efficiency makes them one of the most attractive ways of separating oil and water. Over the years, better products and processes have resulted in a great reduction in the demulsifier concentration required. This trend is still continuing.

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A short survey of the chemicals used to demulsify crude oil emulsions since the beginning of the century

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Size exclusion chromatogramms of a polyester amine and starting products

In spite of a plentiful range there is still a need for more efficient demulsifiers and finishing agents. The new demulsifiers are best described as "polyester-amines"; they are obtained by polycondensation of: 1. an EO-PO-block copolymer 2. an oxalkylated fatty amine and 3. a dicarboxylic acid These effective demulsifiers are not clearly defined molecules but rather polymers with a broad molecular weight distribution. With this chemical" box of blocks" it is possible to construct or to tailor demulsifiers for nearly all problems in crude oil dehydration and desalting. In nearly all cases the demulsifier is injected into the continuous phase, the oil phase. Its activity and effectiveness are then determined by two basic functions: speed of migration to the interface performance at the interface. A demulsifier should therefore have a certain defined oil solubility. Speed of migration can be improved by choosing the right carrier for the base emulsion breaker. Performance at the interface depends entirely on the nature of the emulsion breaker. Demulsifiers for oilfields producing with a high water cut should be dispersible in water and oil but sufficiently oil soluble so that enough demulsifier is available for subsequent treatment, as for example later dehydration and desalting steps. Although there are general purpose demulsifier bases suitable for practically all oilfield emulsions, optimum and cost effective resolution of the emulsion calls for an individually formulated blend adapted to specific field requirements.

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Selection of optimum demulsfier

On site evaluation of demulsifiers.

Effective Dissolvan demulsifiers. left: w/o emulsion + traces of free water. right: separated phases: oil and water.

Developed by Clariant for field use: Dissolvan test kit for testing, blending and selecting demulsifiers on sire.

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Attempts to characterize and classify oilfield emulsions so as to find common factors and similarities for optimum selection of a prospective demulsifier are still in their infancy. Until the secrets of oilfield emulsions are unlocked, emulsion breaking will remain highly empirical, and closer to an art than a science. With so many factors influencing the stability of an emulsion, each individual oilfield obviously requires an approach very closely tailored to prevailing conditions. Although evaluation methods and procedures are rather basic and simple, there is no standard universal screening test other than the "bottle test". This means that evaluation of promising demulsifiers is only as good as the test performed and the interpretation of results. Wherever possible, tests must reproduce actual field conditions such as temperatures, agitation, residence time, water content, oil properties and flow pattern.

The field technician will often have to make up new formulations on-the-spot in order to meet the desired requirements of spontaneous emulsion breaking clean interface complete dehydration satisfactory desalting efficient solids rem oval clean separated water.

Determination of residual salt in treated crude oil.

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Detailed laboratory screening of existing demulsifiers and new research products at varying parameters such as

-blending ratios -solvents -mixing intensity -rate of injection -treating temperature -settling time Once a selected blend delivers encouraging results in the field laboratory, a full-scale field trial must be performed to confirm that effective separation of oil and water at low cost and low temperatures is realized dry oil and clean water are produced with a minimum of sludge at the interface product costs are reasonable handling and storage of the product are simple and safe. During the life of an oilfield the properties of the oil and the ratios of water and emulsion undergo continuous changes. As the water cut increases, longer retention time is needed for the water phase; corrosion and scale inhibitors, oxygen scavengers and biocides may have to be injected. And as the oilfield reaches depletion, enhanced recovery programs may be implemented, making emulsions more difficult to treat. At the same time newer Dissolvan blends will become available. It is important, therefore, to periodically revise the original demulsifier choice in order to maintain top performance and cost effectiveness.

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The synergy of well-matched criteria:

Wet oil treatment with time, chemicals, agitation, heat, electricity

The "nodding donkey" relentlessly pumps the oil to the surface.

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Demulsifier Injection, Time and Agitation

Where to inject the demulsifier depends on pipeline gathering systems, dehydration facilities, retention time, crude oil characteristics and demulsifier properties. With short residence time in the treating plant, the injection should generally be as close as possible to the producing wells; in event of longer residence time, the demulsifier could be injected closer to the central treating plant. A demulsifier injection rate and thorough mixing and distribution in the oil stream proportional to oil production volume usually results in better and more economical treatment. However, sufficient agitation should be provided for complete destabilization of the produced emulsion before any phase separation takes place. To understand and calculate the existing mixing energy, the Reynolds Number NRE provides a guideline.

Turbulent flow is essential not only for optimum distribution of the demulsifier to destabilize the emulsion, but also for necessary coalescence of the dispersed water particles. While oil and free water flowing together with associated gas do not allow exact determination of flow behavior, it can be assumed that turbulence will start with Reynolds Numbers above 2300. In systems where large quantities of free water are produced, it is preferable to inject the demulsifier after the free water knockout vessel to avoid possible losses of demulsifier with the water and to minimize hydrocarbons drained with the water.

Monitoring a large scale field-test with a blend of Dissolvan demulsifiers.

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The Effect of Heat The application of heat is very often essential to obtain fast resolution of an oilfield emulsion. Heat reduces the viscosity of the oil phase (continuous phase), thus increasing rate of diffusion of the demulsifier to the interface and permitting quicker settling of the water droplets. In addition, the paraffin waxes and asphaltene compounds present at the water drop lets/ oil interface may melt and redissolve. Once back in solution they no longer exhibit any stabilizing effect on the interface and water droplet coalescence can occur.

Theoretical heat requirement to increase the temperature of 1 bbl of fluid by lF or 1 m3 fluid by lC

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Viscosity reduction of the oil phase is achieved only by heat. Higher temperatures entail many disadvantages such as the loss of lighter hydrocarbons, the need for additional equipment and higher operating costs. To a certain extent chemicals can substitute for heat requirements, making oil treatment at lower temperature more economical. The viscosity of a stable emulsion of given oil and water quality rises with increased water content. Depending on the emulsifiers present in the crude oil, stable emulsions are found even up to 70% v/v basic sediments and water (BS&W).

The Influence of Viscosity Investigations of various oilfield emulsions show that water drop let sizes follow a distribution curve pattern and can be as small as 1 pm. It is known that larger drop lets will fall faster in the oil. Knowing the oil viscosity and the specific gravity difference between oil and water, the rate of fall, V, can be calculated according to Stokes' Law.

Viscosity of emulsions with different water contents.

Two interrelated physical effects are important to understand how water separation is affected in practice: reduced oil viscosity increases the water settling rate linearly increase in water drop let size accelerates the settling rate exponentially. - 20 -

Higher volumes of water will flow as free water. In practice, a build-up of wellhead and line pressures is observed with the increasing water cut during the production life of a well. By destabilizing the emulsion and generating bigger drop lets, demulsifiers injected into the well or flow lines help reduce these pressures. Coincidently, the deposition of paraffins and asphaltenes is impeded or even reversed. In some cases these paraffinic and asphaltenic deposits can even be removed by interaction with the demulsifier. When this oil reaches the first stage in the treating plant, the lower viscosity contributes to better degassing.

Electrical Dehydration, Desalting and Time Dehydration of crude oil by batch treatment requires long settling times, high capital investments and large areas for the processing equipment. U se of electricity speeds the settling process even more than heat, and allows smaller vessels and higher throughputs than settling and wash tanks. However, it has been found that the action of the electrical field is limited by the water content in the oil. At lower temperatures dehydration rates can be slow and of no practical use because of excessively high oil viscosity. Therefore the use of electrical units is often restricted to final desalting with he at in one or more stages after primary dehydration. Once the original water content has been sufficiently lowered, the oil coming from the last settling vessel is mixed with 2 -8% v/v of fresh water and occasionally additional demulsifier to dilute the salt water drop lets and to redissolve any salt crystals.

Theoretical salt content in crude oil (salt crystals excluded) with different quantities and salinities of water. Paraffin-bound salt crystal in oil.

A modern and efficient way of dehydration and desalting wet crude oil: the electrical desalter.

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The Effect of Fresh Water on Salinity The salinity of produced waters varies from essentially zero to saturation; however, it ranges typically from 20000 to 150000 ppm chloride salts of sodium (NaCl), calcium (CaCl2), magnesium (MgCl2) and others. In the general shipping analysis all salts are reported as equivalent to sodium chloride (equ. NaCl). A typical formation water salinity may be 170000 ppm equ. N aCl. The BS&W content of 0.9% v/v after presettling means a salt content in the crude oil of 1700 -2000 ppm (600 -700 ptb::-) equ. NaCl, which is far in excess of the required shipping specification. How salt content can be reduced by electrical treatment is illustrated by the following practical field data:

*ptb = pounds per thousand barrels - 22 -

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Crude oil desalting in the refinery

Crude oil desalting in the refinery.

Crude oil received by the refinery contains a variety of water-soluble contaminants including chlorides, sulphides and bicarbonates. In addition sand, silt, rust and tar can also be present, together with residual formation water and water picked up during transportation and storage. These impurities must be removed to prevent corrosion, plugging and catalyst contamination in process units. For this purpose, dehydration and desalting equipment is placed upstream of the furnace and the distillation units. Desalting can be achieved by the less efficient thermal dehydration method, or by electrical desalters.

The des alter is essentially a large, wellinsulated vessel in which salts and other contaminants settle out und er turbulencefree conditions aided by an electrical field. The fundamental technique in refinery desalting is the application of an effective water wash, which intimately contacts the crude oil and the residual salt water. The washing process starts up-stream of the desalter, where 3 -7% v/v clean water is added and then emulsified at the mixing valve with the crude. Salt crystals are dissolved, sediment containing water particles and trace contaminants drop out in the des alter as water particles coalesce and settle. Wash water will remove the majority of watersoluble contaminants, particularly the salts, which otherwise would be responsible for down-stream corrosion and fouling.

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The electrical field induces dipoles in the small water droplets; that leads to attraction, coalescence and accelerated gravity separation.

During the degassing of wet crude oil partial evaporation of water occurs, especially at elevated temperature. A given volume of water can be dispersed in either a few large of many small drop lets.

The smaller the salt water droplets, the larger the total surface area and the higher the vapor pressure. Often due to evaporation salt saturation is exceeded and salt crystals are formed.

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Crudes in a refinery des alter will sometimes require no extra demulsifier beyond the residual from field treatment. Often, however, a wellchosen demulsifier can enhance the efficiency of the unit, permitting more complete water separation, thus removing more salts and giving a lower water cut in the desalted crude. Of great importance is the quality of the drained water. Oil content is affected not so much by the height of the water/oil interface in the vessel as by the action of a well-selected demulsifier. In the refinery situation the demulsifier has in practice the function of dehydrating and desalting the crude while simultaneously deoiling the waste water. Because of higher temperatures and pressures, demulsifier selection is by other techniques than the conventional bottle test, such as studying the behavior of the emulsion in an electrical field or conducting various emulsion stability tests. Intimate knowledge of the chemistry and known performance of the numerous bases available further facilitates this selection. No matter how unique the properties and requirements of a particular crude may be, Hoechst is committed to aid in selection of the best possible demulsifier through the expertise of its process and laboratory specialists. Moreover, Hoechst is also committed to developing newer and better bases to meet the challenges of today and tomorrow.

The changing salt content of a degassed wet crude oil during the water separation process. Larger water droplets with "lower salinity" settle faster than smaller droplets with "higher salinity".

Final desalting in the refinery. Removal of residual salt with wash water is indispensable prior to distillation.

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Deoilers their role in oil production

Effluent waters of oil treatment and refinery processes have to be environmentally safe. Dismulgan deoilers and appropriate techniques are the guarantee.

Clarification of effluent waters in oilfields and refineries is becoming more and more essential. With pollution a major environmental concern, efforts are concentrated on the reduction of oil and turbidity in water disposal systems, and the possibility of recycling the water for reinjection.

Dismulgan reverse demulsifiers from Hoechst are specifically designed for the clarification of oilcontaining effluent waters and for the treatment of oil-in-water emulsions, i.e. emulsions in which the oil exists as a fine dispersion in water, which is the continuous phase. Choosing the right water clarification process and the corresponding chemicals required for an optimum solution is not easy. Therefore a large number of clarification aids are available, ranging from inorganic salts, through acids and coagulants, to flocculants and surfactants.

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Effluent waters of oil treatment and refinery processes have to be environmentally safe. Dismulgan deoilers and appropriate techniques are the guarantee.

Prior to field application, laboratory evaluation is necessary to select the most suitable compounds. The test procedure will depend mainly on the existing water treating system, actual field parameters, mode of application and type of chemicals. This procedure provides for a better determination, and differentiation of the products' performance and yields an indication of treatment rates.

The most common and reliable test procedures used are the bottle shaking method, stirrers, dynamic coalesces and flotation cells. During field testing, the products will be screened either undiluted, or as solutions in organic solvents or water. Common to all tests is a continuous monitoring of speed of sedimentation and/ or accumulation of oil on the surface, clarity of the water, pH, floc size and oil redispersion effects.

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The flare, an essential safety device in oilfield operations.

Very often the oil-containing waters do not respond to chemical treatment und er lab conditions. Therefore a combination of physical means, such as aeration, and chemicals should be used. Here again, inorganic and organic compounds, together or in sequence, have to be applied in order to obtain a satisfactory response. In practice, the mechanical equipment installed consists of: retention vessels for gravity settling and/ or skimming coalescer pipes coalescer vessels filters API and CPI separators flotation cells and cyclones. Frequently, however, the required degree of purification is achieved only in combination with appropriate chemicals. The chemical engineer has to use a combination of testing procedures to evaluate, establish and verify chemical performance by means of coalescence, coagulation, agglomeration, skimming, settling, floating, filtering and absorbing. Last but not least, he contributes his extensive experience as the reliable basis for cost efficient recommendations and resolutions of water clarification problems. Today and in the future, Hoechst will further perfect these oilfield processes with research, products and technical service.

Countless pumps producing from a steam soak oil sand.

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A central dehydration plant for treating wet oil from different reservoirs.

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Engineering data

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Improved Dismulgan deoilers separate the oil from the water with ever greater economy.

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Conversion of viscosity units.

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