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    Commercial Emulsion Breaking

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    Hugo Enríquez
    Emulsiones en la Industria Petrolera y como romperlas

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    Commercial Emulsion Breaking

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    Hugo Enríquez
    15 views14 pages
    Emulsiones en la Industria Petrolera y como romperlas

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    © © All Rights Reserved

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    Emulsiones en la Industria Petrolera y como romperlas

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    © All Rights Reserved
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    Download as pdf
    15 views14 pages

    Commercial Emulsion Breaking

    Uploaded by

    Hugo Enríquez
    Emulsiones en la Industria Petrolera y como romperlas

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    © All Rights Reserved
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    ‘operation and adequate emulsion life, Methods are available for the forma ttn of emulsions wth desired properties for efficient pipeline op Further development of emulsion transport technology is dependent sos Kitna sce chore tremens cnc bem onde oil and potential shortages of diluent. Commercial operation of an emulsion transport system is required to determine the long-term technical and eco- nomic viability of this technology References 1. Of Gasp. 1072, 217 51 E Mase 8:5 oon §.0: OW Gat. 1074, 101), 24 4 Simon Royse WC. resented tthe rs Anal Meeting ofthe Sct Povclsun Ragnen of motean esate of Maing Motalesgel wd Poe Icam Engine, Sata barbara CA. 1068 paper SPE at 4, Simon: Poyter W. Gr) Fe Teche 1068, 20, 130. x 5. Ronen Mj. Serer td ntefecel Phenomona; Wiley: New York, 178 pp pease 6, Nonion Surfactant Schick M. , Ea Surfactant Sclence Seley Deer Now York oe Var [RECEIVED for review December 18, 1990. ACCEFTED reviséd manuscript June M4, 1991 VIII Commercial Emulsion Breaking Richard Grace Naleo Canada Ine. 3464 78th Avenuc, Edmonton, Alberts, Canada T6B 2X9 Ths cheptors purposes to share the qualitticeperspctic of ema sion braking hl by the petroleum Industry ths peoducion oe = roning portions eel Incorporation of sterpepe en sr = stoidad infor of broader conceptual information te cmp thas cach commercial acity mast be eee a nigh detopeg = eruloon breaking goals and methods. Theor of eaten demulinion, erably of app chemical, sad letchene of present demir wlecton techniques ee presened Thc cept reinforces the ba thatoguatato view of emulsion beak ssn at thi tine forthe petrol ind. neste roof ‘erable edaced, pial by studing each creel ie, or crude ol a unigu cave If tach study ts ronooncey foc sald model for preictingemulton-reakingprforsones na developed and spied on # elder sea Bvversionsor on ano waren areone of matyproblens rectly aso ated with the petroleum industry, in both ole prodecton eet nee, environments. Whether these emusons ae erated inate a, unavoidable, a in the ill production area, or are dlibontchy eset as in refinery desaling operations, the economic nssesoty ey anaes emulsions or maximize olkwater separation is present, Pegho a sconomics of el-water separation dette the kor eon ete dedicated to this issue. Before we describe the methods and economics of emulsion breaking at commercial face cepts concorning emulsion and the pote ‘will restate several key con- Industry Emulsions and Demulsification Theory of Emulsions. An emalsion isa mixture of two immiscible liquids, one of which is disperse ‘das droplets in the other. For the petroleum 0065-2998/92/0231-0919 $07.75/0 © 1902 American Chemical Society BU'D YD industry, the two liquids are usually crude oils or refined hydrocarbon prod- ucts and water. The presence of water in erude-ol systems isa part ofthe production from oil wells. Most producing wells wll produce water and oil simaltancously at some point in thelr life spans, ether asa result of natural formation conditions or as an effect of secondary or tertiary production smethods. Within the refining industry, water i either present asa result of water contamination present in the erude oil, induced into the crude oll to ‘wash’ contaminants from it, or the result of steam injection to improve fractionation, Through a variety of mechanisms an emulsion may form from this oll-water mixture. - Emulsions formed in the petroleum industry are predominantly water in-oil or regular emulsions, in which the oil is the continuous or external phase and the dispersed water droplets form the dispersed or internal phase. Reverse emulsions, or oil-in-water emulsions, ae formed when water con stitutes the continuous phase and oil constitutes the dispersed phase. It is not unusual to find both regular and reverse emulsions occurring together More complex emulsions have also been noted when reverse emulsions exist within the internal phase of a regular emulsion. The complesity of these emulsions may allow many alternating internal-external phases, although these are very rare. A stable emulsion is one that is unable to resolve itself in a defined time period without some form of mechanical or chemical treatment. Three basic conditions must exist before the formation of a stable emulsion occurs 1. Two immiscible liquids must be present. This condition is met by the simultaneous presence of oil and water in many petro- Mistry environments 2. An emulsifying agent must be present to form stable ofl-and- ‘water emulsions (in much the same manner that the normally ‘immiscible combination of oil and vinegar is emulsified by egg. whites to form the stable emulsion, mayonnaise). The type of oil and water emulsion formed is dependent on the type of ‘emulsifying agents present. Emulsfying agents that are more soluble, dispersible, or wettable in or by oil favor the develop- ‘ment of oil as the external phase and hence a water-in-oil emulsion. Emulsifying agents that are more soluble, dispers- ible, or wettable in water favor the development of oil-in- water emulsions. Commonly occurring emulsifying agents found in petroleum emulsions are asphaltenes, resinous sub- stances, oil-soluble organic acids (such as naphthenic acid), finely divided carbonate scales, siliea, clays, metal sulfates, metal sulfides, or chemical additives. These substances usu ally stabilize droplet interfaces between external and internal phases of the emulsion a 67 oragitation must be suppled to the mis ofland water to persone qu thin the other. In gn eral the greater the agitation or energy applied, the teens stable the emulsion, This stability is «real ofthe in droplet size of the internal phase rable, the sum total Theories of Demulsification. Within commercial emulsion breaking, a numberof general rules help to form the basic philosophy of hog emulsions behave: " i Talo 1. Petroleum emulsions are composed ih are composed primarily of immiscible liquids. Separation should be the natural tendency of the liquids, providing a density differential between the hg exists ‘The rate of gravitational settling or rising is dependent on the Surface tension ofthe droplets that form the internal phuse of the emulsion. Large droplets have less surface function of mass than small droplets; therefore, in be done to increase increase the rate of separ anything that droplet size, or coalescence, will 3 Ansgnulon stable within afiven enronment Alt environment may affect the stability of an emulsion allow separation of the phases 4. 4 stable emulsion exists only whe Isifyi e ly when emulsifying agents are resent. Elimination, alteration, or neutralization of the exnul! sifying agents will allow immiscible liquids to separate From these four generalizations it be a i a ‘comes apparent that a number of lion breaking. Any single change in these arcas may weewo we result in the resolution of an emulsion, How these various factors affect ‘emulsion stability is presented in brie as follows, Liseosity. An oil wth «high viscosity has the ability to hold up more and itger water droplets than an ol witha lower viscosity. The viscosity of {nail canbe reduced by the application of heat, the addition ofa diluone or the addition of chemicals. Lowering the viscosity increases buth the sat {rbid settling of the water, Heavier olis typically more diffcult to dehydrate {han light ol as its density is closer to that of water. The density ofthe water E also important; fresh water will tend to separate from oll at slowey stg than salt water Water Percentage. ‘The relative proportion of oil and water afects the stablty ofan emulsion, Ina regular emulsion, the maximum stability of an emulsion will occur at a set ratio of water tool. Typically this mashoncy found at low water percentages as these droplets have a much smaller chance of colliding with other water droplets and coalescing, Increasing the water percentage may destray the stability of an emulsion igs of Emulsion. Stabilities of emulsions generally increase wit age. Qridation: photolysis, evapoation-of light ends, or bacterial action ney increase the ratio of emulsifying agents within an oil. (Light ends are la frolecular weight, low-density hydrocarbons, such as pentane, hexane, aed butane, that will vaporize sylene significantly over te) Breaking ceval ‘ons as soon as possible after emulsion formation will eliminate ovredhes the effects of aging Control of Emulsifying Agents. Emulsilying agents are necessary to create emifeions, The elimination, alteration, or neutralization of these ‘materials alows for resolution or prevention of emulsions, Elimination of ‘emulsifying agents may inchude corrosion inhibition progratns to reduee the amount of iron sulfide available, careful selection of corrosion inhibitors te juoid emulsification tendencies, or elimination of incompatible erude oll fiom erude-oil blends. An incompatible crude-oil blend is one thet, whe, ation of asphaltenes. This precipitation most commonly occurs when an asphaltic crude oil is blended with a paraffin crude oil Alteration of emulsifying agents would include such measures ae Fie Oe On D Be the addition of an asphaltene dispersant to “ti up" sna ttl madifiers to prevent large parallin eefetal fren Agitation Control. M farane. inter mistre wil reduce emulsion stably ne re performance Parameters in Production and Refining tions With entts Petroleum industry, emulsion of el and water may t ‘of oil and water may be associated With every stage of production, transportation refining. The extent of Smuttifeation and the economic impact of cuntaort ‘ssociated with rag ans in hydrocarbon processing equipment wildens an what treat- ee methods if any, are necessary to prothice desired k lrocarbon specifica tions. An understanding of the impel a a emulsification on key \complete Processing areas is required. The pritne 1. hydrocarbon dehydration 2. inorganic solids and salt removal 5: effluent or produced.water quality 4. oll-water interface control 5. treating temperatures ay ttcader sense, these area of concern can be divided into oduct Soccer ny Hees, ad energy consrraton aes goal ote Valid for both the oil producer and refines, ths Product quality Beal of each portion of the oll industry may not be synergistic. Fentucers and refiners tend to view demulsifcger, erformance pa. ‘umeters from the following perspective Oil Dehydration. Oi production companies must be able to bri basic sediment and water (BS&W) as determined by a standard BS&W test (ASTM D 96) or a variation ofthis test. Pipeline specifications for water content are needed for a variety of reasons, Among these are the refiner’s need for a predictable and high quality of raw materials, the desire of the pipeline company to reduce corrosion potential by eliminating the electrolyte (water) from the corrosion process, and the desire of the pipeline company to construct pipelines on the basis of their eapacity to deliver marketable hydrocarbon produets rather than waste materials Failure by the oil producer to meet pipeline specifica tions for any extended period of time will result in the pipeline compaiiy refusing to accept produced oil. This outcome alone forces the oil producer to ensure that emulsions are resolved to reduce BSE&W in ol to. 0.5% or less. Producers pay pipeline tariffs according to their BS&W content, so that reductions in BS&W below 0.5% reduce the cost of transporting their prod- uct to market. If each reduction in BS&W below 0.5% is less than the costs necessary to achieve the new BS&W standard, the oil producer will pursue that standard. Within the.refining environment, the field of erude-oil dehydration is viewed someshat differently. The first process a crude ol (or blend of erade oils) is subjected to isthe desalting process. This process was developed with the expectation that a crude oil will have a known water content (less than 0.5%) and a soluble inorganic ehloride salts content associated with this water (formation waters from oil-ield production may have salt contents approaching 300,000 mg/L). Salts may also occur in erysalline form dis- persed within the ol. As these salts have considerable negative effects in the downstream processes of the refinery, itis desirable to remove them. ‘This salt reTmoval is accomplished by injecting a relatively fresh water (typically 3-8% of the crude-cil volume) into the crude-oil charge line to extract the salt or “wash’” the oil. (The charge lin is the line that transfers crude oil from storage or pipeline through preheat exchangers to the de- salter vessel.) The more thorough the contact ofthe water with the crude ol the higher the potential for extracting salts. Hence, agitation is usually applied valves or in-line static mixers to promote thorough mixing ‘This agitation usually ereates an emulsion. The separation of the oil and water phases then takes place in a desalting vessel or treater. ‘A problem may occur here in that the separation of oil and water may not be complete by the time the oil exits the desalter on its way to an atmospheric fractionation unit. Any water that remains with the crude oil will have to be heated to atmospheric fractionator inlet temperature, typi- cally 290-370°C. ‘This requirement provides a significant cost in fuel gas to heat the water. ‘Ata 20,000-m’/day refinery with a desalter outlet temperature of 100 °C and a crude-oil heater outlet temperature of 315°C, each tenth of a percent of water carryover will result in 20,000 kg of water being heated 215 superheated steam, If voy high amounts of water carryover are present, the expansion of the steam, once it enters the fractionator, may damage the vessel. Incomplete dehydration will also reduce dezalting efficiency as the salts are earried into the system with the excess water. Refiners typically attempt to limit water carryover to 0.2% in light crude oils and 0.4% in heavy ‘erude oils by attempting to fully resolve emulsions within the desalter Inorganic Solids and Salt Removal. For the oil producer, the diving fore forthe remaval of nog sais antl feet stottios nine getty etn of a ae rial inna wild end wae pean ment of proct The removal of « mort of salts evvally socomplaked asa ae iees of ape excess water from the crude oil. This removal necessitates disposal of the produced water by the producer. Typical, spon is accomplished through deep disposal wells Gr water Rood injec, tion wells. Deep-well disposal is viable only in certain regions because of envroamotl aera reasons Teeth ee eso Sit cl and covoion pac ma sleds Spun gunn, Hetoral pode nce sent ‘quantities of inorganie solids than does light-ol prodaston ee Set Iptiag wheats oteshane tetera noun cine fo vary of Fens Agee han Pe cont ated pred nd igh qual Th pln oy ok of tot argc ody Sen solace meses maze ten of mechan par ese by sede Containg Share Ships inden pesaleoa se Le ‘The oil producer, on the other hand, must dispose of any solids removed fom an onto aes pl ce ek Teed fill area), shipment to an approved waste facility, the solids, which is directly related to emulsion-breaking capabilities and the amount of solids present. In many cases it may be desirable for an oil producer to blend a portion of oil-wet solids into shipments for pipeline if the specification of less than 0.5% BS&W is not exceeded. This method of solids disposal may be the most cosf effective available to the producer The refiner’s position on inorghnic solids and salt removal is that as ef these contaminants (ais cost-effective) should he removed from + incoming crude oil into the wash water by the desalting process. Excess chord ss become ata potions that promote exer aay sumption or reduce conversion in the eracking and treating processes, Chilo. ride salts also compromise the rekabilty of refinery overheads whose, bo, ‘cause of hydrolysis upon heating, they form highly corrosive hydrochloric acid in the overhead system. (The refinery overhead isthe equipment, such a ers, accumulators, reflux equipm 3, that is used to ‘condense hydrocarbons and water vaporized in a fractionation column and ‘exiting from the top of the column.) Chloride salt also cause fouling, which restricts refinery run lengths or aggravates corrosion. The economics of salt removal are very complicated. A salt content of less than 2.85 gfm®(1Ib/1000 barrels) is a common refinery target for desalted crude oil, although this target varies considerably from ste to site. Prime modifiers to this target are desalting equipment available and type of crude-oil stock processed. ‘The removal of inorganic solids is also important to the refiner. By cfficient emulsion breaking at the desalter, the refiner can expect to signif- ‘eantly reduce the amount of solids carried through the desalter into the downstream refining units. Inorganic solids removal of 80% or greater is a typical base standard, although this amount varies greatly with each refiner, the type of separation equipment available, and the crude oils involved. Tnorganic solids have numerous detrimental effects on the refiner. As with chloride salts, many solids (especially metal-containing solids) may ‘poison catalysts and thereby increase catalyst consumption or reduce con- ‘version of hydrocarbons. Solids may act as foulants or promote reactions that ‘create fouling, which restricts heat transfer or run lengths in exchangers and furnaces. Excess solids may reduce the product quality of residual fuels or coke. Solids may aso promote foaming and fouling in fractionators, which in tum may restrict throughput or induce use of antifoams. All of these effects usualy occur simultaneously in an integrated refinery, Accurate calculations fon the economic impact of inorganic solids are extremely complicated and difficult to perform, although such calculations can be the prime justifica- tion for improving desalter operation. Refiners may dispose of removed inorganic solids by land farming, shipment to approved waste-disposal facil ties, or disposal to the water-handling system. Effluent Water Quality. When resolving emulsions in the petro. leum industry, water is always produced. In some areas the goals of the refiner and oil producer are identical in effluent water quality. Both refiner and producer want to minimize the amount of oil in the water systems, a5 this represents either lost product, increased capital, or increased operating costs to recover the oil from the water. The costs of not achieving complete ‘il-watey separation the first time in a desalter or oilfield treater are re- flected f the need fr equipment suchas water kim tank, water lration equipment, various flotation units, clarifiers, settling ponds, biox units, and ‘accumulated-cil treating facilities in water-disposal systems. Each of these ‘units wll have significant operating costs above and beyond the capital costs. (A bior unit is a basin, pond, or vessel where biological activity digests organic materials such as hydrocarbons carried with the water charged to the unit.) Oil producers will typically set standards for oil-n.water content rang {ng from less than 10 ppm in very light erude oils to several hundred parts per million in very heavy crude oils. These specifications are usually‘site- specific and are dependent on equipment available and crude-oil type. Oil producers in Canada usually have the advantage of disposal wells or water- flood schemes in which produced water is disposed. Failure to meet self- {imposed oil-in-water limits usually results in loss of hydrocarbon product back to the formation, For an oil production facility that disposes of 1000 m? ‘of water per day with an oll content of 1000 ppm, 365 m of ol is lost per year. ‘At $25 (Canadian) per barrel, this amount of oll translates to a product loss ‘worth approximately $57,000 per year, plus any maintenance costs and well stimulation costs to restore injectivity lost as a result of formation plugging from oil-wet solids. Oil-wet solids in water-lood systems may damage for ‘mation permeability and reduce recovery i: In the Canadian refining industry, only refineries in the western prov {nces have access to disposal wells for produced water. Their concerns are similar to those mentioned with the oil producers. In other areas of the country, effluent waters must be-treated to a standard that will allow for discharge to the environment. The typical standard for allowable cil water content is less than 10 ppm. fication may result in fines, shutdown, offending refiner. ure to consistently achieve this speci- ind poor public perception of the Oil-Water Interface Control. In any petroleum processing unit in which emulsions are resolved am interface between al and water mst ‘oceur. The quality of this interface ig directly related to the efficiency of emulsification in either a refinery desalter or an oilfield free-water knock out or treater. The sharper the transition between clean water and clean oil (or the tightness of the interface), the better the ability to control oil and water retention times and quality and operate the vessel. Broad transitions between oil and water are usually the result of (1) incomplete resaution ofthe emulsion (2) allure of an emulson-treatng rogram to resolve emulsions caused by one or more specific emulsifying ‘gents, () exces or incompatible eating chemlenl (2) bale olan solid, (5) buildups of insoluble organic materials such as para asphaltenes, or (6) any combination thereof. With a broad interface (" ‘cuff’, or “pad” layer) present, evel-sensing equipment and water dumps may operate incorrectly or malfunction, and thereby divert water to clean-oil outlets and cil to water outlets. Electrostatic grids may short out ifthe pad (usually high in water content) makes contact with the grids. Emulsion pads also occupy space within a treating vessel and promote channeling, which affects the retention time of a vessel. Concentration of polar hydrocarbons, ‘emulsifying agents, and solids usually occurs in interface “pads”. These molecules have a high tendency to be dispersed in the water phase, become concentrated through oil-in-water recovery processes, and recycled, upset the vessel to further aggravate emulsion treatment. In general, emulsion pads limit the performance of emulsion-breaking equipment and chemicals. Both refiners and oil producers view large emul sion pads as symptoms of inefficient emulsion treatment. Ifthe emulsion pad can be eliminated, performance in all aspects of emulsion breaking should improve. Treating Temperature. Treating temperatures may have signif- cant impacts on both refinery and oll production emulsion-breaking pro- cesses. In general, the higher the temperature, the greater the ability to resolve emulsions; however, increases in treating temperature affect many other factors negatively. In the refinery desalter the range of treating tem- peratures available is limited by plant design. Heating of the crude oil up to

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