chemical and atmospheric resistance as well as the adhesion to the substrate of the underlying film. Extender pigments are relatively inexpensive compared to color pigments and are easily incorporated into @ coating. Most are white or near-white inorganic minerals with a coarser particle size and lower oll absorption (binder demand) than primary pigments, Extender pigments include fillers, such as calcium carbonate, Mica, hydrous and kaolin, Plasticizers Not all coatings contain plasticizers. However many coatings require the addition of one or more plasticizers to enhance flexibility, extensibility and toughness to coatings. TYPES OF COATINGS & CURING MECHANISM, Resin is a polymer, made by combining single units (Monomers) of chemical compounds, such as styrene, vinyl, phenols, urea, aldehydes and ethyl acrylate. In the presence of a catalyst and at elevated temperature, the monomers unite will be activated and polymerized with one another to form molecules which are many times larger. When only one kind of monomers Is used the produced resin is 0 called Homopolymer. If two or more kinds of monomers are used, the resin is called Copolymer. Degree of polymerization is a very important feature of a resin. The greater the resign molecular ‘weight, the greater the hardness, the better resistance to chemicals and solvent and the longer service ‘durability, On the negative side, the higher the molecular weight the higher the viscosity and the less the wettability. With the advance in paint making technology, there are many types of paint products available in the market. Paints are classified in many ways, either by the generic type of the binder,by service, by function but the most commonly used classification Is by the drying and curing mechanism. Three distinct drying/curing mechanisms are known to the industry and paints are accordingly grouped. Drying and Curing Mechanism + Oxidation drying paint ‘+ Solvent evaporation drying paint ‘+ Polymerization curing paint ‘SURFACE PREPARATION OBJECTIVES Proper surface preparation is vital to the long life and effectiveness of a coating applied in corrosive service. A coating with strong adhesion will have a longer life and greater resistance to corrosion than ‘one, which has marginal adhesion. If adhesion is weak, the coating will gradually fail by blistering, under film corrosion, or chipping and flaking. The actual purpose of surface preparation has two-fold purpose. The first purpose is to remove any extraneous, loose materials and other surface contamination from the surface of the substrate, as well {as to eliminate chemically bonded scales, oxide films, and similar surface products that cover active adhesion sites on the metal surface. The removal of such materials exposes the reactive sites so that the coating can develop the maximum adhesion. The second purpose of surface preparation is to increase the surface area by increasing the roughness and anchor pattem of the surface. This means that the actual exposed surface area per unit area is greatly increased. By increasing this effective surface, many additional reactive sites on the metal surface are exposed, allowing for polar or chemical adhesion of the primer to the surface. ADHESION ‘One industry that has been especially concerned with proper adhesion is the automotive industry. Very seldom, if ever, does the original coating on the body of an automobile blister, peel, alligator, or ‘otherwise delaminate from the surface. This represents a considerable achievement when one considers that there is probably no other piece of expensive equipment that is exposed to such varied and harsh conditions as automobiles. It is subject to rain, storms, snow, and dust, as well as industrial ‘atmospheres and sodium chloride from deicing salts. In spite of this, there are very few failures of the Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009exterior coating. The excellence of automotive finishes and their resistance to severe weather and chemical atmospheres can be attributed to meticulous surface preparation. ‘TYPES OF ADHESION ‘The type of adhesive bond depends on both the substrate and the coating. The three types of adhesive bonds are: * Chemical, * Polar * Mechanical ‘SURFACE PREPARATION STANDARDS Many surface preparation techniques are used to clean the surface and thus provide proper coating adhesion, The Steel Structures Painting Council “SSPC* and National Association of Corrosion Engineers “NACE” has done extensive work in developing necessary surface preparation standards. The surface preparation standards outlined by both the SSPC and NACE are listed hereafter in a descending order of effectiveness. Each grade lower in the list allows a greater amount of con- tamination to be left on the surface prior to coating. This is extremely important since it is the level of contamination that is the key to coating adhesion. Surface Preparation standards (NACE,SSPC & ISO 1. White Sandblast - NACE # 1, SSPC SP 5-63 Near-White Sandblast - NACE #2, SSPC SP 10-63, Commercial Blast - NACE # 3, SSPC SP 6-63 Acid Pickling - SSPC SP 8-63 Brush Blast - NACE # 4, SSPC SP 7-63, Flame Clean and Power Sanding - SSPC SP 4-63 Power Tool Cleaning - SSPC SP 3-63 ‘Chip and Hand Wire Brush - SSPC SP 2-63 Solvent cleaning - SSPC SP 1-63 penarawn ‘The amount of time, work, and effort required to achieve any particular degree of surface preparation depends to a great degree on the initial condition of the surface to be cleaned. It is necessary to take into account the amount of rust, old paint, contamination, and active corrosion or pitting on the surface to be protected. While there are many different initial conditions, the degree of surface ‘cleanliness following surface preparation can be divided into nine main classifications, as outlined by ‘SPC under Surface Preparation Specification. SURFACE PREPARATION TECHNIQUES ‘The advancement of surface preparation methods paralleled the development of high-performance protective coatings. First were the vinyls, which, in order to obtain optimal performance, needed a thoroughly cleaned surface. Inorganic zinc coatings added impetus to the proper surface preparation techniques, as well as the addition of epoxies, polyurethanes, and some of the heavy epoxy surfacers. Tt was also found, after surface preparation techniques were developed, that the old standby coatings, such as red lead, oil, asphalts, and coal tars also performed better and longer over a properly prepared surface. High Pressure Water jetting High Pressure Water jetting relies on the use of water at very high pressure, i.e., 6000 to 12,000 psi or more, producing a transit velocity of 350-400 meters per second, This kind of pressure rapidly removes most’ contaminants from a surface and is particularly effective in the removal of heavy mastic-type ‘Copyright © Hudson Technology & Strategic Studles, Ottawa-Canada 2009‘materials that have failed and under which corrosion exists. It is effective in removing accumulated salts, dirt, grease, and other similar contaminating materials from surfaces. It should be clearly understood that while water blasting will remove the majority of heavy rust scale where tubercles have formed, it is not capable to produce an anchor pattern (Peaks & Valleys). It is also considered a better and faster cleaning method than mechanical tools for deformed steel plate, expanded metal gratings, and similar areas. Abrasive Blasting The preferred method for preparing steel for the application of high-performance coatings is abrasive blast cleaning technique. It not only provides a clean surface and removes rust, scale, oil, paint, and similar contaminating materials, but it also roughens the surface and provides mechanical as well as chemical and polar adhesion sites for the coating. Abrasive blast cleaning is based essentially of im- acting the surface with high-velocity abrasive particles to such an extent that the contamination on the surface is removed and a clean, active metal surface is obtained. There are essentially five methods by which the abrasive particles can be accelerated to obtain sufficient impact to cut the metal surface. These are Dry air blasting, Water abrasive blasting, Wet abrasive blasting vacuum blasting and Mechanical rotary blasting. The first four methods are hand methods of blasting, while the fifth is an automated method and is primarily an in plant operation. All hand methods may be used to prepare surfaces on location or wherever abrasive blasting is permitted. Dry Air Blasting Air blasting has been the most common and effective method of surface preparation, particularly for ‘coatings that are to be used in highly corrosive areas. Many different abrasives may be used with this blasting procedure, and it may be used for blasting ships, industrial structural steel, concrete and many other different surfaces. It is the most versatile type of surface preparation and undoubtedly involves the lowest cost of any surface preparation method besides the rotary blast method. The principal advantage of an air blast system Is that the blasted surface is dry all the time. While it can be blasted to a number of different degrees, depending on surface cleanliness requirements. Unless there is considerable humidity in the area, the surface will remain dry until the coating is applied, which is usually done on the same day. The disadvantage of dry sandblasting is primarily the dust cloud generated as a result of the breakup of the particles of sand or grit. Water Abrasive Blasting ‘The distinct advantage of water abrasive blasting is the elimination of dust during the operation, However, there is considerable buildup of water in the area, which also can be a hazard, The surface produced by water abrasive blast unit using high-pressure water and a relatively small amount of abrasive Is good and provides a good profile. The environmental agencies are much happier with a water blast setup than a dry blast. The high-pressure water blast cleans by the action of both the high- pressure water and the contained abrasive propelled by the high-velocity water. There is also a much greater water-to-abrasive ratio than in the wet blast technique. In this method, the blast surface is ‘wet, which Is also a distinct disadvantage. Wet Blasting The wet blast system uses essentially the dry blast methods, equipment, and techniques, except that there is a modified nozzle where little amount of water is injected into the blast stream. There is a ‘much smaller water-to-abrasive ratio in this wet abrasive blast method than in the water abrasive blast system, Because of the smaller water content in the blast stream, considerable amounts of the abrasive can accumulate on the surface, making it necessary in most cases to wash the surface before the application of any coatings. Again, rusting takes place rapidly unless inhibitors are used both in the wash and in the blasting operation. Where inhibitors are Involved and high-performance coatings are needed, every care must be taken to determine whether the coating will satisfactorily adhere to the inhibited surface. Many inhibitors interfere with coating adhesion. Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Vacuum Blasting Vacuum blasting is principally a dry blasting operation, also called closed re-circulating blast systems, is a method to do away with the dust and dirt of an open blast system. The results obtainable with a vacuum blast system can be equivalent to the best surface preparation by air or centrifugal wheel blasting. In vacuum blast systems, the blast nozzle is enclosed in a rubber cap or a brush which surrounds the nozzle and which prevents the abrasive from fiying in all directions, This brush or cup is connected to a high-efficiency vacuum mechanism which pulls more air than is used by the biasting nozzle; therefore, ‘as soon as the abrasive strikes the surface and bounces away, it is picked up by the vacuum system and carried back to the blast pot where it is cleaned before being automatically re-circulated through the mechanism, Rotary or Wheel Blasting Rotary blasting Is entirely an in-plant operation where stationary units of rotors are be used to throw abrasives at various steel surfaces, The principal advantage of the rotary blast is that it is dry. The metal can actually be warm before going into the operation, and a watm, dry, clean surface is a definite advantage for the application of coatings. Since materials are handled mechanically, the Production can be fast, using either metallic grit, shot, malleable iron or wire cuts. In many rotary blast setups, the prime coat is also automatically applied within a few feet of the blast unit so that the steel Is coated almost immediately following the surface preparation, which is also an advantage. Because of the closed blasting chamber, any dust or air pollution from such units is automatically eliminated and collected in a special dust bags through suction blowers and preciptators so that no contaminants escape into the atmosphere. ‘The major limitation of the rotary blasting process is that steel must be blasted in its original state and ‘not after fabrication. The nature and shape of the work has a great effect upon the practicality of the ‘operation. Highly irregular, large surfaces such as shop fabricated beams are difficult to clean in the usual set-up. ABRASIVE MATERIALS. There are a number of significant factors involved in the abrasive blasting of steel. Of particular Importance from the standpoint of coating application and effectiveness, is the material or blasting media used to clean the surface. These can include any number of various grades of sand (e.g., river ‘of quartz sand), as well as synthetic grits or those made from refractory slags and steel grit or shot. Each of these materials will clean the surface in a different way and to a different degree, and will Provide a different surface profile. Martensitic, austenitic and duplex stainless steels require greater care in preparation for coating ‘compared to carbon steel. Iron-free grit must be used to clean and profile such surfaces, Any residual iron introduced into the steel surface would corrode to produce ferric chloride that would initiate pitting of the stainless steel. To avoid iron contamination aluminum based abrasive is used though garnet is now becoming more widely used. Garnet is much harder than aluminum oxide and therefore more effective and it is also environmentally less deleterious. ‘Types of Abrasives + Synthetic Nonmetallic Silica-Free + Siliceous + Chilled Cast tron * Crushed Steel Cut + Steel Wire * Aluminum Shot * Silicon Carbide Aluminum ‘Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009* Oxide Refractory Slag (Coal & Copper Slag) + Garnet Quartz Si COATINGS APPLICATION “The purpose of coating application is to develop a continious protective layer of material of a specific ttickness which firmly adhere to the substrate, while providing the desired resistance to the surrounding environment. The achievement of this purpose must take into consideration many additional factors which will be discussed individually. ‘Successful coating job stands on four main factors namely ‘Comprehensive and clear specification Proper Material selection Successful Surface preparation Successful coatings application ‘Well established Inspection and QA/QC protocol If any one of the five factors may collapses the entire application will be a failure and there is no compromise and the results will be less than satisfactory. If the specification is not clear, fully understood, accepted by all parties, material is ineffective or wrongly specified, surface preparation and pretreatment are less than satisfactory, coatings application doesn't satisfy the specification/ Manufacturer requirements, the QA/QC procedures are not followed and comply with the specification requirements, the overall coating protection will never be achieved and catastrophic failure will be reached soon. APPLICATION METHODS “There are a number of application methods by which coatings can be applied. The three principal methods are by brush, roller, or spray. Other methods consist of paint pad applicators, electrostatic spray, electroplating, dipping, and fluidized bed coating. Of the three principal methods, brushing is the slowest and spraying Is by far the fastest. Good paint application equipment is like a good tool of any kind, its essential for the proper application of coatings, Many coatings applicators use the wrong ‘spray equipment or worn nozzles and then cannot understand the reason for their poor results, ‘TYPES OF COATING SYSTEMS Protective coating system can be achieved in many ways as shown in the diagram below. Single-Coat Systems Single-coat systems is the most commonly used when a short life is all that Is required, such as when structural steel is coated at the mill to protect it until it can be properly blast cleaned and coated later fat the construction site. When it is applied for purely decorative reasons, such as in painting the interior of a house or office building. When the coating has been specifically formulated for one-coat application, as with coal-tar urethane or certain types of zinc-rich coatings or glass flakes reinforces resins ( Polyester, Vinyl ester & Epoxy) Multiple Coat System Multiple-coat systems may consist of: ‘More than one coat of the same coating material generally applied in contrasting colors. ‘The use of multiple layers coat is the basis for the "impermeable coating concept’. All organic coatings ‘are permeable to some degree. Anti-permeable coatings contain no materials that will react with moisture. Each ingredient is designed to be unaffected by moisture and acts only to allow the moisture vapor to accumulate within the coating to the point of normal moisture absorption content. ‘An impervious coating must be impervious to air, oxygen, carbon dioxide, and the passage of electrons Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009and ions. An impervious coating forms an inert barrier over the surface. This type of coating is most often used in immersion service and must be inert to surrounding chemicals. This coating must have hhigh dielectric strength, must have good adhesion to the underlying surface and must be able to wet the surface well enough to prevent any voids at the coating substrate interface. One or more applications of different types of coatings This is the type of system most frequently found in structural steel applications such as on offshore installations, which generally have two or three and occasionally four different types of coatings. An ‘example of this type of system is a zinc rich primer with epoxy topcoats, or with epoxy intermediate and a urethane topcoat. Primers are often known by the name of their pigmentation, since the pigment plays significant, active role in the coating. ‘A primer is the first coating applied to the work piece. The functions of a primer are: ‘+ To adhere to the substrate ‘+ To provide a base or key for subsequent applications of coatings ‘+ To protect the substrate against corrosion by acting as a corrosion inhibitor, a barrier coating, or a sacrificial coating INTERMEDIATE COATS (MID-COATS) The mid-coats in a multicoat system are typically added to the system to improve the barrier characteristics of the system. All organic coatings are permeable to some extent and will allow some passage of water vapor, oxygen, and other vapors through the cured coating film. Naturally, some Tesins have better properties in this respect than others. Most coating systems will become more permeable as the amount of pigmentation is increased. ‘The materials used for mid-coats often are modified by the addition of certain pigments (e.g., lamellar or flake-like pigments) to increase their resistance to water permeation. Their coverage may also be improved by the use of inert fillers and thickening agents to give high-build properties. FINISH COATS Finish coats are often chosen for their appearance as good color retention, low levels of chalking, and gloss. A smooth finish is necessary to discourage the retention of surface contamination and to allow rain to wash deposits away, which benefits both appearance and corrosion resistance. ‘A smooth finish is best achieved by using small quantities of nodular-type pigments. In some ‘exposures, increased chemical or solvent resistance may be beneficial if it can be achieved by selecting the correct finish coat. Finish coats can also be formulated to provide good resistance to the ultraviolet (UV) to minimize degradation of the resin binder. SCREENING AND QUALITY CONTROL OF COATINGS Tt may be somewhat difficult to understand why it is necessary to test individual coatings in a generic type, even though they supposedly have been manufactured for similar exposures. Actually, there are hundreds of different formulations for any specific generic type of coating. Some manufacturers will take a standard formulation published either in a governmental specification and manufacture the ‘coating according to that standard. Other manufacturers will use those standards as a starting point, and then spend considerable research time determining the best combination of ingredients within that generic type of material that will do the best job. COATING DEFECTS AND FAILURE CODES Paint is an expandable material that is used to protect or decorate another material more costly to replace; and the best paint for any application is the one, which can offer optimum service during the longest period of service. Eventually failure of any paint is inevitable; but rapid deterioration of a coating is undesirable and can be prevented or at least reduced by careful observation of good painting practices. It has been estimated that at least 65% of all coating failure have resulted from Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009reasons related to surface preparation, therefore, care in the surface preparation, application and inspection is the best assurance against coating failure. ‘The coating manufacturer retains samples of each batch of coating made, but the prudent owner, coating engineer, or inspector may also choose to keep a sample of any coatings used for future reference. Analysis of formulation problems is much easier with a wet sample of coating than with dry flakes. Coating failure or applied film defects may be grouped as follows :- ‘+ Defects related to the coating formulation ‘+ Defects related to the coating selection ( Improper specification ) + Defects related to surface preparation + Defects arising during application STRUCTURAL DESIGN AND THE COATING PERFORMANCE A large part of expensive service failures due to corrosion would not occur if proper precautions were taken during the design stage of structures, equipment and plants. Some design may be adequate from a strictly engineering standpoint, but can soon lead to costly maintenance and even steel replacement because of poor design for proper coating application. Structural steel shapes almost always pose coating problems, particularly those in smaller areas. Unfortunately, they represent a basic building material and therefore, in many cases, must be used regardless of the coating difficulties they create. These basic structural shapes consist of the angle, channel, H-beam, and I-beamn. + Steel Shapes * Sharp Edges ‘+ Rivets and Bolts © Bolted Joints + Welds © Seal Welds © Weld Flux © Skip Welds © Lap Welding + Brackets and Hold downs + Back-to-Back Angles * Box Beams + Water Pockets and Recesses * Flanges + Staiways + Open Grating * Pipe Supports * Blind Openings + Bimetallic coupling + Welding & design changes during construction TECHNICAL SPECIFICATIONS & CODE OF PRACTICE Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009A coating specification is a formal document that tells the contractor what to do and where to do it, but generally doesn’t tell him how to do it.” Coating specifications are normally tailored to meet the requirements for a particular job, and they ‘come in many forms and in various degrees of details and clarity. Sometimes a coating specification is, so vague as to defy interpretation by anyone, sometimes induding the person who wrote it. A well- prepared specification will go a long way to make a job go smoothly and to ensure that all parties are pleased as the owner gets a good job and is happy, and the contractor makes money. The coating specification is the inspector's guideline to the coating job. Before any coating job starts, the coating inspector should: * Obtain and read every part of the specification + Make certain that he has a complete and accurate understanding of the specification * Clarify with the owner's representative, any aspects of the coating specification which might seem inaccurate or impractical, or that he does not understand Proper specification is the Key to the job success. A specification that describes the materials needed, the objective(s) of the coating, the key procedures required, the appearance of the finished coating, and the inspection requirements usually assures a good coating job. A poor specification is an invitation to disagreements, possible lawsuits, and, above all, early coating failure. ‘Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Chapter 7 Chemical Treatment Corrosion inhibitors ‘+ Laboratory Evaluation of Corrosion inhibitor performance ‘* Application of Corrosion Inhibitors Microbial Control ( Sulphate-reducing Bacteria ) Classification * Morphology ‘+ Metabolism + Culture Media ‘+ Enumeration of the Bacteria + Water Injection Systems + Origin of Sulfate-reducing Bacteria on the Reservoir + Biocide Selection + Blocide Treatment Alternative Strategies of Bacterial Control Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009CORROSION INHIBITORS ‘A corrosion inhibitor is a substance which, when added to an environment, decreases the rate of attack by the environment on a metal, Inhibitors can be inorganic, organic or polymeric formulations. Passivating inhibitors such as chromates, molybdates, silicates and phosphates form a strong non- corrosive oxide film with steels which causes the surface to be cathodic. Four classes of chemical treatment will be discussed: + Neutralizing chemicals © Oxygen scavengers, * Sulphide scavengers © Organic film-forming inhibitors. Neutralizing Chemicals For oilfield systems in which the aqueous phase is predominantly fresh or condensed water, effective corrosion prevention is possible by raising the pH. This method is particularly effective where acid gases are the primary source of corrosion. Simple alkalis such as sodium hydroxide and ammonia have been used for this application. although more commonly water soluble amines are used including thanolamines, morpholine and cyclohexylamine. One area where the use of neutralization is being increasingly practiced is for the control of wet gas lines corrosion. For many of these systems monoethylene glycol (MEG) is added as a thermodynar hydrate inhibitor and this is an ideal way of delivering the neutralizing chemical. The objective is for the selected chemical to control the pH between 6.5 and 7.5 and thus maximizing the conditions under which protective iron carbonate scale will be formed without moving into an area where there is a significant potential to form other carbonate scale, such as calcium carbonate. ‘Oxygen Scavengers Corrosion of steel! in brine is enhanced by dissolved oxygen. Neutral water of low salt content in ‘equilibrium with air at 70 ° F (21°C) will contain about 9 ppm of dissolved oxygen. The solubility of ‘oxygen in water decreases with increasing salt concentration and temperature. The most commonly used scavengers of oxygen are sodium and ammonium bisulphite solutions. Sodium sulfite, frequently referred to as an oxygen scavenger, has been used for many years to remove dissolved oxygen from boiler feed water and from oilfield waters used in water flooding. Dissolved oxygen is removed in the oxidation of sulfite to sulfate. Theoretically, it requires 7.9 ppm of sodium sulfite to react with one ppm dissolved oxygen. ‘At most surface temperatures, the reaction between sodium sulfite and dissolved oxygen proceeds slowly, but the reaction rate increases as temperature increase. A catalyst such as cobalt and ‘manganese salts usually added which produces nearly instantaneous removal of oxygen. Cobalt gives the greatest increase in reaction rate. Ammonium bisulphite is applied as a liquid (typically 65% strength) and requires no catalyst. Hydrazine is also used as an oxygen scavenger. Its greatest use has been in boiler feed water applications or in the protection of casing from oxygen corrosion. Sulphide Scavengers Sulphide ion is a natural constituent of many produced fluids. The activity of sulphate reducing bacteria, particularly in waterflood operations, is a common source of sulphide. It is not unusual for sweet production systems to turn sour with time as a consequence of reservoir souring. ‘The use of the word ‘sulphide’ implies all three water soluble forms: H.S (in low to neutral pH), HS (neutral to alkaline pH) and S in (alkaline pH). Sulphides are unwanted constituents of crude oil and water. Their presence in the separated crude has a detrimental effect on the sales value of crude and performance of refineries. In the acid form, hydrogen sulphide is toxic to health and accelerates corrosion processes. In production systems with natural sour production, CRA’s material is specified to Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009resist the corrosive nature of sulphides. ORGANIC FILM-FORMING INHIBITORS Nitrogenous inhibitors are widely used for corrosion control in crude processing and transportation flow lines. The cationic polar part of the molecule is attracted and chemically adsorbed to the negatively charged sites on the steel surface and the fatty (hydrocarbon) part of the molecule is exposed to the crude oil and acts as a barrier to water. The inhibitor has the affinity to displace any pre-existing water molecules on the steel surface (lower interaction energy). By replacing and repelling water away from the metal surfaces, the oil films are able to stifle corrosion much like other physical barriers such as paints. Certain hydrocarbon components of the crude will also co-adsorb with the inhibitor to improve the barrier effect. Inhibitor efficiency increases with concentration until the surface is saturated, i.e. it has adsorbed inhibitor molecules on all available sites. The efficient use of organic inhibitors depends on prior removal of oxygen from the system. Organic corrosion inhibitors degrade at high temperature and lose some or all their effectiveness. Cationic nitrogenous inhibitors include the following groups of chemicals; Fatty amines and quaternaries Primary, Secondary, Tertiary and Quaternary Diamines Amides Ethoxylated amines Imidazolines Corrosion inhibitors are sometimes classified according to their water / oll solubility and dispersabilty characteristics. e.g. + Oil soluble © Water soluble Oil soluble/water dispersible ‘+ Water soluble/oil dispersible ‘The classification refers to the dispersability of the formulation. The solubility characteristics of an inhibitor within its formulated "package’ will show little or no relationship to the solubility characteristics ‘once the inhibitor ‘package’ is injected into the corrosive fluids. The active inhibitor is a surfactant and has specific properties of adsorption and partitioning. When a corrosion inhibitor formulation is dosed to a crude oil flowline, the surfactant inhibitors are freed from the solubility constraints of the formulated inhibitor package. Each component of that formulation is now present at a much lower concentration within the crude oil fluids. Partitioning of these components between the cil and brine phases will occur in a manner that is not always predictable. LABORATORY EVALUATION OF CORROSION INHIBITOR PERFORMANCE To select the best corrosion inhibitors a thorough procedure is usually required, starting with screening tests in the laboratory followed by field testing. There is no such thing as a universal corrosion inhibitor and selection of optimum inhibitor is fleld specific with performance varying according to field water composition, dissolved gases, temperature, flow rate, flow regime etc. Normal procedure is to identify four or five satisfactory inhibitors from laboratory screening testing while eliminating any that is obviously of poor performance or not compatible with other field chemicals followed by ranking against their efficiency performance after field trials. ‘The normal strategy for evaluating inhibitors is to begin with a high dose (more than sufficient to protect the system) and then to reduce the dose in steps until the threshold level is reached. This corresponds to the minimum concentration that provides acceptable protection. In the field itis normal to apply a higher dose than the laboratory determined threshold value. ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009A range of laboratory test proces is available. One major difficulty is to simulate the dynamic Ins under which corrosion could occur in the field. Laboratory screening tests are normally followed by field tral of the shot listed produce for 1-2 months each inthe same stream. A series of foam pigs are send in the system between successive chemicals to remove the corrosion protection film of the former chemical. The following seven laboratory tests are commonly used by most testing institution for the screening purposed, the bubble testis the first screening test among others which are described as follows:- + Bubble Test «Rotating Cylinder Electrode » Autoclave tests ‘Static Weight Loss Test (steel coupon) » Weight Loss by Wheel! Test Film Persistence - Using the Wheel Test Principle Recirculation Flow Loop APPLICATION OF CORROSION INHIBITORS Continuous Treatment It is operationally desirable to apply corrosion inhibitors continuously as far upstream of the problem area as possible. Initially it may be desirable to dose the inhibitor at a concentration in excess of that normally required so as to establish good film coverage. Thereafter a rate of 5-100 ppm would be necessary, according to the corrosively of the fluids. Continuous treatment through an injection line is the preferred method of treatment to give reliable corrosion control. For downhole application Corrosion inhibitors can be pumped via a macaroni or kill string where well ‘completions allow. If a bottom hole injection valve is fitted, then solution of corrosion (typically 2 10% solution in diesel or condensate) is placed in the annulus and make-up inhibitor solution added with a suitable pump. Injecting corrosion inhibitor via a bottom hole injection valve is ‘semi-continuous, but generally produces more satisfactory results than other intermittent treatments. Bull heading technique is widely used to protect the subsurface equipment where there is a risk of formation damage. It involves the displacement of the produced fluid with a high concentration slug of inhibitor (e.g., 10%) in hydrocarbon solvent to the production string. Enough volume is used to fill the ‘tubing and the well is shut in for a limited period of time, ideally for 24 hours before being put back on production. Batch Treatment Batch treatment of flowlines Is a proven technique where a calculated slug of neat or diluted corrosion inhibitor travel through the entire length of the pipeline is contained between two cup or Bi-directional pigs. Batch treating of oil or gas wells involves the use of a calculated volume of a corrosion inhibitor, ‘either neat or as a solution/dispersion in solvent/water. Weighted sticks were used in low producing wells containing reasonable amounts of water. The sticks are dropped into the well, sink to its base where they slowly dissolve into the producing fluids. ‘Squeeze Treatment Squeeze treatment technique is to displace corrosion inhibitor/ solvent mixtures into the tubing with a high pressure pump, followed by several tubing volumes of over-flush, such that the inhibitor solution penetrates 3-4 feet into the formation matrix at the periphery of the well bore. Core compatibility must be established prior to treatment design and application. After a pre defined soaking interval the Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009inhibitor is allowed to be adsorbed to the surfaces of grains in the formation and siowly produced back into the well bore as the well is back to production. Treatment lifetimes of good squeeze are much longer than batch treatments. Squeezing of corrosion inhibitor can be carried out as a 10% solution in diesel (for example) with pre-flush. A typical treatment would require 100 barrels of corrosion inhibitor with an over-flush of additional 300 barrels. With Squeeze operations it is particularly important that the inhibitor does not ‘gunk’ as a result of the evaporation of the solvent package as this would result in formation damage. There is also a potential risk of emulsion block formation. Microbial Control ( Sulphate-reducing Bacteria ) “The impact of bacterial activity on petroleum production operation is little understood in spite of the serious damage caused by these organisms, The sulphate-reducing bacteria SRB are considered to be an ancient species of organism having developed some 2,000 million years ago and occur in most soils and waters. Conditions within many reservoirs and most pipelines are not adverse to survival and growth of the SRB. Various strains can tolerate pressures from atmospheric to about 500 bar, temperatures from 0 to 75 °C, pH from 5 to 9.5 and salinities form 0 to 23% sodium chloride. ‘Common features are growth only under anaerobic conditions and the ability to activate and reduce sulphate to sulphide via a dissimilatory pathway. All sulphate-reducing bacteria are strict anaerobes, requiring not only the absence of oxygen for growth but also a low redox potential of around -100 mV or less. The reduction of oxidized sulphur compounds is the main method of energy conservation. Sulphate is generally required, although alternative electron acceptors are known. ‘SRB are widespread in both aquatic and terrestrial habitats; especially anaerobic mud and sediments ‘of brackish and marine environments. Once bacteria colonize they tend to bury themselves in a polymeric mass produced during their metabolism called the Bio-film. Bio-film provide shelter to bacteria from antagonists in their environment and allow effective extraction of nutrant materials to permit a thriving culture of bacteria. There are a large number of other bacteria that can reduce sulphite, thiosulphate and elemental sulphur but not sulphate, via dissimilatory pathways, to sulphide. WATER INJECTION SYSTEMS In general, any water system containing sulfate has the potential to support the growth of sulfate- reducing bacteria. Thus, in offshore systems, the potential for growth of sulfate-reducing bacteria exists within water injection systems, production systems and fire water systems. The pipelines cannot be either sterilized or maintained sterile. Problems related to bacterial growth and sulfide production in each of the systems manifest themselves in different ways. The SRB and other organisms are introduced into the pipeline during hydrotesting and service. Slop oil tanks are generally contaminated by SRB as they contain high levels of seawater and other waste materials. Microbial induced corrosion is the primary cause of corrosion damage in the water injection networks, Most water injection systems operate under the same basic design for the topside facilities; from lift pumps to wellheads. In most cases, however, the flowlines topside represents only a small part of the total water injection system when subsea flowlines and downhole tubular are considered. It is important, therefore, to appreciate that even low levels of bacterial contamination evident in the topside facilities may be indicative of much greater bacterial growth at sites in the water injection system remote from the platform, With respect to bacterial problems, a water injection system can be divided into three distinct parts, ‘* Upstream of Vacuum Tower ‘+ Vacuum Tower to wellheads ‘+ Downstream of wellheads Bacterial control in water injection systems is normally accomplished using two bactericide treatments techniques. Firstly, chlorination upstream of the deaerator and, secondly, organic bactericide into, or downstream of the deaerator. The most commonly used organic bactericides in water injection systems in seawater systems are solutions of gluteraldehyde, formaldehyde or THPS; blended with ‘some other agent e.g. a quaternary ammonium compound to give a surfactant action, Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009In many cases, therefore, even water injection systems presently being treated with proven bactericides, are badly contaminated with bacteria. The growth of sulfate-reducing bacteria in seawater injection systems can result in a number of costly problems. ‘+ Corrosion damage ‘+ Formation Plugging ‘+ Reservoir Souring Corrosion damage “The activity of sulfate-reducing bacteria can induce pitting corrosion on mild steel. In many seawater injection systems iron sulfides have been found among other corrosion products and the presence of sulfate-reducing bacteria identified, thus implicating them in the corrosion process, In water injection Pipelines the SRB colonies are distributed more widely around the pipeline. In severe cases pits may Tink up to form roughly continuous channels of corrosion along the bottom of the pipeline ( 6 O'clock position). Loss of integrity may therefore occur by either perforation or bursting. The sulfides produced by SRB activity and their rate of pitting attack are similar to those formed in sour fluids. Formation Plugging Particulate matter in the injection water downstream of the filters will eventually be deposited on the formation face. Corrosion products including Iron sulfides are insoluble and, therefore, their presence in injection systems is indicative of a potential problem. Bio-film and other organic matter generated as microbial byproduct may be displaced from the pipelines during routine pigging operation or during the course of periodic biocides injection may be accumulated in large amounts and be deposited into the formation. In many reservoirs, significant losses in wells injectivity due to plugging with corrosion products and organic matters were experienced particularly in tight formations. The production of slime by some bacteria may cause problems of plugging and loss of filter performance if itis allowed to proceed unchecked. Slime forming bacteria are normally associated with bacterial bio-films. Reservoir Souring ‘There were enough evidences from close monitoring of the quality of water delivered to the reservoir to maintain the reservoir pressure that a good number of SRB bacteria are swept to the reservoir When seawater Is Injected, there is always concer that this may lead to the growth of sulfate- reducing bacteria and other types of bacteria; initially in the injection wellbore and ultimately deep within the formation itself. The growth of the bacteria in the reservoir causes souring of the associated gas and this may be sufficient to turn a sweet production system into a sour system in a relatively short time. Cases have been recorded of initial hydrogen sulphide concentrations increasing from 1 - 2 ppm to 10, 000 ppm. {tis almost universal that injection water contains SRB when introduced to the reservoir for secondary recovery. These bacteria will be subjected to higher pressure that prevails and also to higher temperature, The injection of the deareated cold sea water into the formation can provide a number of key elements to promote microbiological HzS generation. The cooling effect of the sea water reduces the temperature of the rock around the injector within the thermal viability limits of life of these micro organisms. The deareated sea water is poised at suitable reducing condition for an aerobic sulphate reducing bacteria and the abundance of sulphate (3200 me/liters) supplies the reducible sulphur source, The pH of the seawater or the sea water/aquifer water mix is within the optimum range for microbial activity. Finally, the seawater is rich in sulphate for bacterial reduction, moreover, it lacks the necessary organic carbon for growth where as the reverse is true for the down hole prior to water injection. ORIGIN OF SULFATE-REDUCING BACTERIA ON THE RESERVOIR The origin of sulfate-reducing bacteria in oil-bearing reservoirs is a matter of considerable debate. The means of introducing bacteria to the reservoir are: ‘+ Indigenous - Bacteria were always present. Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘© Drilling - Contamination of the drill mud by bacteria. ‘+ Waterfiood — Introduced via contaminated injection water. BIOCIDE SELECTION Blocides are selected through a series of screening and testing program. Candidate chemicals are tested against a standard population of bacteria (usually 10’ -10" cells/ml) to identify the optimum concentration required to kill. Whenever possible a population representing that present in the pipeline should be used. A range of biocides concentrations are used against the standard population and the surviving bacteria evaluated at intervals over the test which is normally done over a 24-hour period. These are termed time-to-kill tests and are used to identify the combined effect of concentration and time, Sometimes these tests are repeated using bio-fouled steel samples to determine the effect of the biocide on sessile bacteria which is a function of the penetration power of the biocide. From this data it is possible to identify a suitable biocide regime, concentration and time of contact. The bactericidal effectiveness of a chemical is normally determined by exposing cultures of bacteria to the chemical at a range of concentrations and observes the reduction in bacterial numbers over time. If this can be done under carefully standardized conditions then it is possible that the results will be accurate and reproducible, The value of any chemical as @ bacteridde depends on a number of factors which include the following ; + Highly effective against wide range of bacteria at low concentration. + Safe to handle and non-corrosive, + Not inactivated by extraneous materials. * Surface active with good wetting and penetrating characteristics. «Stable on storage. + Readily available and low cost. «Completely bactericidal within a ‘short time’ and not inducing bacteriostasis, ‘+ Fall within the toxicity limit established by the local/ International low. No single bactericide has all of the above ideal properties. Some bactericides are more effective against certain species of bacteria than they are against others. Some may show excellent ‘effectiveness against suspensions of pure cultures in the test tube but show little or no efficiency when dosed into operational industrial systems where they are presented with a wide range of bacterial types and extraneous organic matter. It is important, therefore, that during selection of a chemical to be used as a bactericide in an offshore system the optimum use should be made of all available data ‘on that chemical. ‘A compatibility check on the biocide with other oil field chemicals may also be necessary. Other factors that may be relevant are the discharge limitations related to environmental sensitivity of the site, safety issues in handling/ storage and the thermal stability. Many biocides are acidic with high surface activity and this may interfere with the persistent and adsorption of the corrosion inhibitors. This adverse behaviour of biocides can be overcome by increasing the corrosion inhibitor dosage rate subsequent to a biocide treatment for a period sufficient for the inhibitor film to reform, typically 4 times the normal doze for 24-48 hours. BIOCIDE TREATMENT ‘Commercial biocides act in several ways. Chlorine and chlorine dioxide oxidize organic material and this includes bacterial cells. Organo-bromines, bisthiocyanates, phosphonium salts and quaternary ammonium salts attack the bacteria cell membrane to become permeable and hence leak its essential fluids, Aldehydes (acrolein, formaldehyde and glutaraldehyde) are fixatives and cause the cell wall to become impermeable such that the bacteria suffocate. Some systems are treated with water soluble, oil dispersible, mixture of biocides, which may include a surfactant into the formulation (usually a quaternary ammonium compound), The surfactant function is Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009to increase penetration of the biocides Into slimes and deposits. There appears to be little evidence that this occurs during the short exposure period of the pipeline to the slug of biocide. Aldehydes, phosphonium slats and quaternary ammonium salts are used for water injection pipelines either as single formulations or as blends. There is a belief that bacteria rapidly adapt itself with particular biocides, accordingly it is recommended to varying the biocide type/formulations periodically so, bacteria can not develop its immune system and dominant species of bacteria is prevented. SRB can also flourish in water injection flowiines. Here the nutrient is supplied by the body fluids of the cocopods, algae, diatoms and other organisms from the seawater. These small creatures are broken up in the seawater intake pumps and the solids removed in the filtration system. The soluble components remain in the seawater. To keep the water quality reasonable and reduce the internal corrosion of the flowlines the system shall be treated with biocide weekly or twice weekly. For oil pipelines the biocides are normally added as slug does though there has been some use of continuous dosing. The biocide slug is best introduced between lead and trail spheres or poly-pigs. The slug dose size is often limited by logistics but should be sufficient to ensure that the bacteria on the pipeline wall are exposed to a sufficiently high concentration of biocide for enough period to ensure an effective Kill. To this end the biocide will need to be evaluated by time-to-kill testing. Tt is important that the treatment regime is adjusted to accommodate the length of the pipeline (and the flow rate) such that adequate concentrations of biocide are present at the far end of the pipeline. Antibacterial Chemicals No single method of bacterial control is universal for all oilfields as each situation presents its own peculiar problems. There are two major classes of anti-bacterial chemical in use in the oilfield, the oxidizing (chlorine, bromine, etc.) and the organic non-oxidizing bactericides. Oxidizing Bactericides The oxidizing bactericide most commonly encountered in the offshore oilfield is chlorine. Chlorine and hypochlorite are used to treat raw seawater to control macro-fouling in the intake pipeline winning pumps. These oxidizing chemicals are not very effective against SRB in flowlines because of the iron sulphide saturated slime that surrounds the bacteria, protecting the cells membrane and allow no ‘access to the chlorine gas to penetrate. The residual concentrations of chlorine allowed into water injection flowlines downstream of the water injection treatment plant should be kept at minimal as severe pitting corrosion may be caused at high level of concentration, Chlorine is normally generated electrolytically by passing an electric current through seawater to generate hypochlorite which will be then pumped into the system. Chlorine may also be added as solid sodium hypochlorite but this Is normally only done in closed or semi-open systems, i.e. tanks, flooded members, etc. ‘As with other disinfectants the effectiveness of chlorine treatments is also a function of time and temperature. A residence time of up to thirty minutes might be required to achieve a complete kill. Increases in temperature and residence time will, therefore, increase the efficiency of the kill achieved. ‘A major problem with chlorine treatments is the fact that chlorine will react with and become consumed by organic matter (Cholrine demand). Non-Oxidizing Bactericides Large ranges of organic compounds that exhibit bactericidal action are commonly used in oilfield system. Selected types are: ‘Aldehydes (Formaldehydes & Gluteraldehydes) Quaternary Ammonium Compounds Amines and diamines Imidazolines THPS Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘© Isothiazolones ALTERNATIVE STRATEGIES OF BACTERIAL CONTROL ‘A range of control procedures as alternatives to the use of organic bactericides has been suggested, particularly for water injection systems. In some cases these have been put into practice with varying degrees of success. + Chlorination - downstream of deaerators. Oxidation via aeration. + Ultraviolet Radiation. + Xray Radiation. + Phage. + Nitrate treatment. Chlorination ‘The re-injection of chlorine downstream of the deaerator in water injection systems has been practiced jn some offshore systems, This Is a cheap alternative to organic bactericides and allows continuous treatment, There are, however, several drawbacks, and therefore, its use may not be possible in all systems. Chlorine will, due to its oxidizing nature, promote corrosion of mild steel. The levels of chlorine injected must, therefore, be carefully monitored and controlled. Furthermore, continuous chlorine treatment will exclude the use of oxygen scavengers and, therefore, the system will be susceptible to oxygen ingress. Chlorine levels are normally maintained above 0.3 - 0.4 ppm. Oxidation As a control measure against sulfate-reducing bacteria alone, aeration In some systems may provide a cheap and very effective treatment. Obviously, its use is limited to areas where oxygen corrosion is not a problem, e.g. concrete or coated structures. Aeration has been used as a means of removal of dissolved sulfide from stagnant water and as a means of preventing further sulfide production in that system. It can been shown, however, that although the bulk phase of a system may be aerobic, sulfate-reducing bacteria can survive in bio-films on surfaces in oxygenated system, being protected from oxygen by the activity of aerobic heterotrophic bacteria, Ultra-violet Radiation Ultra-violet (UV) sterilizers technique for water Injection has received a great deal of attention over the past few years, UV radiation has a wavelength that lies between the blue region of the visible spectrum and the X-ray region. Only wavelengths greater than 200 nm have a significant bactericidal effect; with maximum efficiency being seen at 265 nm. Radiation alters the chemical structure of the nuclear material of the cell (DNA), therefore cells will not be able to divide. In common with chemical bactericides a finite residence time is required in order for the treatment to be effective. X-ray Radiation X-rays have remarked penetration power which makes the sterilization of water 2 possible option. However, it is unlikely to implement the X ray sterilization technique at Industrial level due to inherent safety problems in handling isotopes. Phage “The use of phage (viruses which attack bacteria) to control bacteria in industrial systems has also been proposed however, it was proven not practical. There are significant problems involved in operating a biological control measure such as this, which make its current use impractical, Different phages are specific for different bacteria, thus, it would be essential to identify target species of bacteria, Bacteria ‘can become resistant to phage and, therefore, a range of phage would have to be developed. Nitrate Treatment Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘The use of nitrate as a means of controlling the activity of sulfate-reducing bacteria and removing hydrogen sulfide from various industrial systems is well documented. Recently, the application of this and related technologies has been proposed (and trials performed) for use in oilfield situations. Nitrate technologies may provide a cost effective and efficient means of controlling sulfate-reducing bacteria and remediating hydrogen sulfide contaminated systems, avoiding the use of expensive and environmentally unacceptable bactericides. ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Mineral Scale Formation Occurrence of Scale Formation of Mineral Scales + Formation of Calclum Carbonate scale + Formation Barium and Strontium Sulphate scale + Formation of Calcium Sulphate Scale + Formation of Iron Scale Scale Prediction Modeling Scale Inhibition Scale Inhibition Processes Scale Inhibitor Selection Scale Inhibitor Application Deployment techniques Downhole Squeeze Model Overview Scale Removal ‘Chemistry of Scale Dissotvers Application of Scale Dissolvers Radioactive Scale Identification of Mineral Scales Analysis & Sample Acquisition ‘Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘THE PROBLEM OF SCALE FORMATION IN OIL FIELDS The deposition of mineral scales and sludge in oil production equipment or within the reservoir is a ‘common and potentially serious problem in most oil fields. The deposition of scale on tubular surfaces reduces the fluid flow by reducing cross-sectional area and increasing surface roughness. Fluid flow within reservoir is restricted due to blockage of pores. On heat exchanger, deposition of scales on the metal surfaces reduced heat transfer properties and result in efficiency declines. One possible ‘advantage is reduced corrosion on tubular due to the formation of a thin layer of calcium carbonate, however uneven films result in severe localized (pitting) corrosion. The need to maintain high rates of oll production makes scale formation a serious problem. Many operators had used aquifer dump flood to maintain the reservoir pressure without the need for ‘expensive topside water flooding installations. In many of the old aquifer flooded reservoir extensive Calcium Carbonate /Sulphate Scales precipitate was physically detected at the annulus and at other areas where the two waters get mixed together. Problems in new injectors are caused by incompatibility between the injection water (seawater or ‘aquifer water) and the formation water. The potential for scale formation decreases soon after the start of injection once the near well bore area has been thoroughly flushed with injection water. Injection water corrosively should be reduced to a minimum level through the proper use of oxygen scavengers, biocides and corrosion inhibitors, however poor housekeeping can result in iron hydroxide r sulphide formation, which can ‘blind’ the face of the formation, OCCURRENCE OF OILFIELD SCALE Mineral Scales found in oil production systems contain inorganic salts such as the sulphates and ‘carbonates of calcium, strontium and barium. Other common constituents are various iron oxides, sulphides and salts. Waxes and asphaltic materials are commonly entrained in deposits and can bind together otherwise as friable solids. Sludge can be described as accumulations of unconsolidated material such as scale fragments, sand, waxes and corrosion products, which are not strongly adhered to surfaces. Carbonate and sulphate minerals deposited from solution once the point of supersaturation is reached with respect to each mineral, usually caused by some change in temperature or pressure or from the consequences of two incompatible brines co-mingling. Iron scales may result from accumulation of corrosion products or be a consequence of the action of sulphate reducing bacteria (SRB). ‘Some situations in which mineral scales are found in oiffeld operations includes:~ «Drilling and Completion, + Reservoirs ‘= Production String Topside Production Facilities Drilling and Completion ‘Although not a major problem it is possible to experience incompatibility between the water based driling fluids, and the formation brine. Completion brines can be rich in caldum and can react with formation water if it is high in bicarbonate, CO2 and sulphate. It is not unusual for caldum sulphate scale to occur in the near wellbore as a result of loss of heavy (Ca) brines to the reservoir whilst itis not possible to predict problems when driling or completing a well in a new field. As soon as representative samples of the field brines are obtained it is possible to check compatibility effects between the driling fluid and the formation brines in the laboratory. More common, is the loss of barium sulphate from a drilling mud fluid to the face of the formation. Wells stimulation using hydrochloric acid (HCI) post completion help very much in removing carbonates, but it has no effect what so ever on sulphate scale if exist. Reservoir Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘The injection of seawater into a formation may result in deposition of scale within the reservoir. If the injection and formation water are not compatible then the extent of deposition will be high; however it is quite likely that only minor mixing will occur at the contact between the two brines. Permeability loss deep in the reservoir is unlikely to be significant. Deposition dose to the producing well is much more problematic, in this turbulent zone where more efficient mixing of potentially incompatible brines. The zone of perforations is the most sensitive region and most likely to be damaged. Reservoir damage can be predicted using scale prediction models which consider the possible liquid- liquid interactions. However, a complete modeling study must take into account liquid-solid interactions such as ion exchange and rock mineral dissolution processes. Production String During well production, formation water passes from the perforations through to the open hole and production string, during which series of pressure drops took place which may lower the solubility of dissolved C02. Increasing saturation and increased water pH can result eventually in depositing calcium carbonate scale within the production string but most particularly at those positions of significant pressure drop. The severity of carbonate deposition depends upon the water chemistry and is aggravated by high drawdown. In reservoir subjected to water injection at some point of the reservoir life, the injection water will ‘breakthrough’ into the producing well.. The consequences of mixing incompatible injection and formation water, are rapid increase in saturation of metal sulphates. Sulphate scaling could occur at the perforations and in the tubular goods. Sulphates are more problematic and less easily removable than carbonates. Topside Production Facilities “The processes that cause scale to occur in tubular may also result in damage in the topside process equipment. Pumps, heat exchangers, valves and filters may require replacing and pipe work and separators may need regular cleaning. Large temperature gradient in the process facility enhances the risk of sulphate type scaling, FORMATION OF MINERAL SCALES The formation of mineral scales and unconsolidated sludge’s from flowing brine solutions occurs in stages. In order for a mineral salt to form a hard, consolidated scale deposits four conditions should be satisfied; ‘+ Super-saturation ‘+ Nucleation & Growth © Precipitation © Contact time ‘Super-saturation ‘Super-saturation is the primary cause of scale formation occurring when a solution contains dissolved materials, which are at higher concentrations than their equilibrium concentration. Solutions can become super-saturated, if changes in conditions such as temperature, pressure and pH or through a change in the concentration of other ions in solution may occur. Some mineral salts may remain at supersaturated concentrations for extended periods of time without formation of crystalline precipitates. From chemical thermodynamics, some crystalline salts require a large amount of eneray in their formation. Until this energy is supplied, or until the requirement for it is lowered, crystals will not precipitate. Scale inhibitors can maintain or increase the amount of energy that a crystal will require for formation so, precipitation will be delayed or retarded. Energetic surfaces such as particulate nucleation sites can reduce the energy required for the crystal to form, or can itself supply that energy. As the level of super-saturation increases the system becomes liable for mineral scale precipitation. Tt Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009must be noted that local conditions of super-saturation (e.g. brine immediately adjacent to very hot surface) can cause scaling even though the bulk average brine composition remains under saturation, Nucleation & Growth Nucleation is the initial formation of a precipitate and is commonly caused by the presence of a foreign crystalline material. This crystalline material promotes the beginnings of crystal growth of the supersaturated species. When the crystals have grown large enough that the Brownian and other forces in the solution can no longer accommodate the mass of the crystals in their aqueous environment, then precipitation will occur. The process is accelerated by the presence of foreign materials on the surfaces of pipe/ vessels walls, welds or the presence of solids particles in solution or ‘other crystalline minerals in the formation or on tubular walls (i.e. a pre-existing scale). Precipitation Precipitation can lead to an adherent scale or a non-adherent precipitate, depending on the conditions at the surface of the newly formed crystal. If surfaces can be deactivated chemically, then the mineral crystals may remain dispersed in the solution and carried through without growth of heavy deposits. Many scale inhibitors perform on this principal. If the surface conditions are not modified, then the microscopic particles may agglomerate to form dense crystalline or polycrystalline mineral deposits. Contact time There is a dynamic equilibrium between existing scale and the constituent ions in solution. Crystal growth of an individual scale mineral can be a rapid process. One millimeter of scale build up per week is not unusual providing the solution phase remains supersaturated. The degree of super-saturation will vary and so a pattern of accelerating and decelerating growth occurs giving a layered aystal structure. The growing cystalline surface is also an excellent site for nucleation of other scaling species and multiple layered scales of varying composition are able to form over a period of time. In many oil fields with harsh scale tendencies a 45-60 days are quite enough to fully block a downhole production tubing of 4 ¥2 “ diameter. The production of silt from the reservoir and corrosion processes ensures that there is a constant supply of suspended solids in produced fluids. As the fluids cools, Wax, Asphaltene and emulsified oil can bind together these solids to form sludge, which accumulate in low energy regions, FORMATION OF CALCIUM CARBONATE SCALE Calcium carbonate scale often takes the form of large translucent crystals that may be discolored by impurities (Orange or Red). Deposits are recognized by being highly crystalline and by their reaction with hydrochloric acid where a strong effervescence of CO, is liberated. ‘The solubility of calcium carbonate in water is very low being much lower than one gram per liter at 20°C under 1 atmosphere CO; pressure. Its solubility is strongly influenced by partial pressure of COz, temperature and concentration of other salts in solution. In single brine it is quite possible for super- saturation and hence precipitation and scaling to occur as a result of system changes (Self Scaling). It is believed that calcium carbonate exists in solution as calcium and bicarbonate ions (not carbonate) and so the precipitation of calcium carbonate is expressed as; Ca (HCOs)2 € > HO + CO, + CaCO; In solution Calcium Carbonate Scale ‘The solubility of calcium carbonate therefore decreases as the partial pressure of CO, decreases. Hence, if CO; is removed from solution then the driving force towards precipitation is increased and more scale precipitation should be expected. This explains why carbonate scale is frequently found at positions associated with a pressure drop as a result of carbon dioxide release from the aqueous phase into the gaseous phase. Temperature is another important factor governing the solubility of calcium carbonate. Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009In most oilfield production systems, local high-pressure differentials or high temperature zones will enhance scale deposition at specific points even though the mean conditions suggest that scale should hot occur. FORMATION OF BARIUM AND STRONTIUM SULPHATE SCALE Barium and strontium sulphate scale deposition is usually the result of two different brines co- mingling; one brine rich in sulphate ions (Typically seawater) and the other rich In alkaline earth ions (Typically produced water). When this happen the solubility product of the mineral sulphate is exceeded and the water becomes supersaturated. This process is generally responsible for the formation of barium and strontium sulphates. Ba* + soz > Baso, Sr* + so? > StSO, From solution A from solution B scale Precipitation The crystal size of Barium and strontium sulphate scales is generally opaque, usually much smaller than the crystal structure for calcium carbonate. The solubility of barium sulphate is about 0.002 gram/liter in distilled water at 25°C, which are about two orders of magnitude less than strontium sulphate and also significantly less than calcium carbonate. The solubility of barium sulphate is so low that in the absence of inhibitor there is almost 100% removal of soluble barium when equal volumes of water mix. A relatively small proportion of the strontium is precipitated as sulphate. Barium and strontium sulphate solubility does increase somewhat in strong electrolytes, Sulphate scales are not attacked by acids. FORMATION OF CALCIUM SULPHATE SCALE In the Arabian Gulf, calcium sulphate scales are very common. Formation water In most reservoirs has exceptional high calcium content @ 20,000 plus, which potentially can precipitate CaSO, scale following sea water mix. Calcium sulphate forms as a result of the co-mingling of incompatible brines of as a result of significant temperature or pressure fluctuations. CaSO, solubility in water is much higher than that of barium or strontium sulphates. Calcium sulphate exists in two common forms; ‘© Gypsum (dihydrate) + Anhydrite ‘The latter being associated with high temperatures (Deep wells). The solubility of the two forms differs and most mathematical models can provide data for either or both forms. The solubility of gypsum (the common form) decreases with temperature above 40 °C and is affected by the concentration of cther jons in solution (magnesium ions concentration in the brine has a large effect). Approximately 2 gram/L calcium sulphate can theoretically be held in distilled water solution at 20°C. FORMATION OF IRON SCALE Tron scales can result from the accumulation of corroded iron (oxides, hydroxides) or can be derived from soluble iron. Formation water commonly contain 1-5 ppm soluble iron and occasionally up to 30 ppm. Naturally occurring iron salts from the reservoir are normally in a soluble ferrous form, although iron that is brought into solution through corrosion of steel equipment could take either ferrous or ferric forms. Regardless of the source of the iron, the deposition of iron scales is dependant upon ‘complex interactions involving sulphide ions, bicarbonate ions, pH, the dissolved oxygen content and the oxidation/reduction balance. Brines that contain dissolved iron can deposit that iron in the form of ferrous carbonate (FeCOs), ferrous or ferric sulphide (FeS), ferrous hydroxide Fe (OH)., ferric hydroxide (Fe(OH)s) and ferric ‘oxides (Fe,03). Certain bacteria as SRB play a role in the conversion of ferrous lons into the poorly soluble ferric hydroxide and sulphides. Ferric hydroxide and ferric sulphide form gelatinous deposits ‘Copyright ® Hudson Technology & Strategic Studles, Ottawa-Canada 2009that can very rapidly plug formation pores. For this reason it is important that injection water is treated adequately to prevent corrosive reactions from happening in the subsea distribution network steel pipes or the subsurface equipment that would result in plugging deposits being formed. Water containing colloidal ferric oxide is red in color and water containing ferrous sulphide is black. The presence of iron Is usually detrimental to the action of sulphate or carbonate mineral scale inhibitors. SCALE PREDICTION MODELING The use of Scale prediction models can identify the occurrence, location and severity of potential scale problems during the well operational lifetime cycle. Prediction Models for Scaling tendencies are based upon thermodynamic solubility concepts. Much work has gone into the mathematical modeling of scale deposition so that the type and degree of mineral deposition can be predicted and remedial steps can be taken before the problem becomes disastrous in the field. ‘Two prediction models are commonly used by most operators and research centers namely:~ ‘© MultiScale@ which was developed at NTNU (Norwegian University of Science and Technology) Institute of Inorganic Chemistry. ‘* Scale Chem. Rev 3.2 (2007) from OLI systems, USA. The associated advantages of performing scale predictions are that calculations can be performed for any given system and the likelihood of scale deposition can be measured in terms of saturation ratio ‘and the calculated theoretical mass of scale deposition (mg/L). Scale predictions can highlight process system areas particularly susceptible to scale deposition, which could only be inspected visually during @ shutdown. Scale prediction models can be used to predict the scaling tendency of any of the following minerals: Sulphates: BaS0,, SrSO,, CaSO, (Gypsum & anhydrite) Carbonates: CaCOs, FeCo; Others: NaCl, FeS “The technical objectives of a scale predictive model is to assess how much scale will form as a result of {a given operation and where it is most likely will form. These objectives can be met through the input ‘of accurate kinetic and thermodynamic data. In order to predict the conditions under which scale- forming minerals may precipitate it is necessary to know how the solubility product of the mineral varies with changes in brine composition, temperature and pressure. Representative produced water samples and accurate laboratory analysis are the key factor for successful modeling. It should be dlearly understood that Predictions are only as good as the data that is fed to them. SCALE INHIBITION ‘The selection of optimum scale inhibitor depends upon many factors, including nature and severity of scaling species, brine pH, temperature profile, brine composition, dosing restrictions and treatment cost. The cost of cleaning or replacing scaled equipment and the ongoing costs of inefficient operation caused by scale deposits can be very high, A typical workover for an offshore well could reach $2,000,000 - 2,250,000 and involve considerable loss of production. Effective chemical scale dissolvers do exist and can be a viable option for scale removal. For the oilfield operator the maxim that prevention is better than cure. Scale control can also be achieved mechanically without the need for inhibitors simply by removing the cations responsible for mineral deposition mainly sulphate. Sulphate can be removed by water softening or by ion exchange technology. In general these technologies are elther expensive or present logistical problems in oilfield operations. Reverse Osmosis removes virtually all ions from solution and so can be utilized for the production of potable water from saline brines. Nano-fitration removes only divalent and multivalent ions and has found particular application for the removal of Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009sulphate from injected seawater, thereby avoiding risks associated with Calcium, Barium and Strontium sulphate scaling in reservoirs. Over 95% of sulphate ions are removed using stat-of art Nano-filtration technology. Another advanced technology is the use of specifically modulated molecular oscillations or lattice oscillations which is entirely different from electric or magnets coils technology. Due to the fact that this technology has been developed empirically, there is still no in-depth scientific explanation. SCALE INHIBITION PROCESSES ‘A wide variety of chemical species have been recommended as inhibitors. Anionic, water dispersible or water soluble surface active molecules such as polyacrylic acid or polyamino-phosphonate are useful for carbonate and sulphate minerals scale inhibition. Scale inhibitors act by interfering with the processes of nucleation and/or by restricting crystal growth by restricting the incidence of nucleation. Inhibitors are broadly dassified as: ‘+ Threshold inhibitors (Crystal growth modifiers, nucleation inhibitors). + Dispersants © Complexing agents Scale Inhibitor Types The two general dasses of scale inhibitor that are in common use in oilfield production systems are Phosphorous-containing compounds and the Polycarboxyiates. ‘SCALE INHIBITOR SELECTION The selection of the optimum scale inhibitor involves extensive laboratory testing many of which should simulate the conditions of the system to be treated. This selection procedure involves both the investigation of inhibitor compatiblity with the water to be treated along with performance testing. Scale inhibitor selection is based upon a number of screening stages which allow the elimination of less effective inhibitor at an early stage and allow the more detailed testing which more cosely simulates field conditions to be carried out upon the best inhibitor. At the laboratory evaluation stage it is best to consider all aspect of a products performance, including stability, compatibility, pumpability, environmental impact and efficiency as part of the overall assessment program. The key is to recommend a scale inhibitor that is suitable for each application and not necessarily the product of highest inhibition values. The testing procedure can be summarized as follows: © Static Jar Test + Dynamic Tube-biocking test * Brine Compatibility test * Core flood test ‘+ Compatibility with other oilfield chemicals and materials of construction. ‘+ Stability (Thermal & Storage) SCALE INHIBITOR APPLICATION Application of scale inhibitors to oilfield systems can be by continuous injection in which case all the above considerations apply. If the application Is by squeeze treatment to the reservoir then adsorption/desorption characteristics should be known as well as the possibility to precipitate under downhole conditions. Interference from other production chemicals must always be considered and fully studied. ‘Two common application techniques for scale inhibition are well established in the oilfield these are: Continuous injection Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘© Squeeze treatments Continuous injection Tt Is understood that although individual well or flow-stream brines may have little or no scaling potential, once co-mingled through process equipment, incompatiilities and scale deposition could ‘occur. Accordingly, these co-mingled brines shall be assessed for scaling potentials. Brine-stressing studies from produced waters throughout the field system shall be routinely undertaken. These studies shall be carried out on a periodic basis, as part of the Risk Identification module of the Corrosion Management strategy, to ensure that any changes in water chemistries are addressed. From jar tests and tube-blocking experiments, suitable scale inhibitors should have been identified and minimum threshold levels determined. It is operationally advisable to apply the inhibitor as far upstream of the identified problematic area. In production wells this usually means in the wellhead area but for adequate contro! of calcium carbonate it Is best to apply the inhibitor upstream of any significant pressure drop such as at the downhole choke. Continuous monitoring of the water chemistry for changes in scaling cations and anions provides an indication of increased or decreased scaling tendency. Squeeze Application ‘Although water production may be essentially nonexistent, it is almost assured that it will increase in time. Alternatively, an arbitrary water cut (€.9., 5% or 10%) may be selected at which time a squeeze would be conducted. Inhibitor selection and squeeze deployment are important during the initial production stages due primarily to formation wettability concerns. The use of an oil soluble or oil dispersible Inhibitor may be required, Consideration is given to the use of specially formulated pre~ flush fluids and/or hydrocarbon over-flush. ‘As water production increases, the situation with respect to squeezes reverts to the more conventional ‘approach using aqueous fluids for pre-flush, main treatment bills and overflush. Certain well conditions may dictate modifications such as a low BHP that requires hydrocarbon or even nitrogen gas as carrier to avoid killing the wells. Selection of an inhibitor is based on effectiveness for a particular scale or scales, thermal stability, solubility, adsorption, and de-sorption characteristics. ‘There is a significant risk that during scale inhibitor squeeze treatments, for example, any asphaltene fouling of the tubular could be disturbed with the result that particles of asphaltenes will blind the well bore resulting in reduced injectivity. Therefore if there is a history of asphaltenes production in a well there Is a need to remove existing deposits scale Inhibitor treatment Is attempted. Two squeeze techniques successfully adopted to deploy the corrosion inhibitor down to the well bore region these are:- Adsorption Squeeze In this case, inhibitor is squeezed as a concentrate, partially adsorbs on reservoir rocks and then desorbs slowly over a period of time as the well is returned to normal production. The preferred objective is to adsorb the maximum proportion of inhibitor in the near well bore region coupled with steady, low adsorption characteristics. ‘Adsorption squeezes offer the lowest risk of damage to the formation but inhibitor losses are high due to irreversible displacement to the reservoir or premature return of non-adsorbed product. These problems are most serious in fractured, poorly consolidated reservoirs characterized by multi pressure zones with cross-flow potential, Precipitation Squeeze ‘A major disadvantage of the adsorption squeeze is that typically 50% of product is irreversibly lost to the formation or is not adsorbed in the near well bore and flows back during the first few hours of production, By conducting a precipitation squeeze a higher proportion of the Inhibitor could be ‘fixed’ in the reservoir and was available for slow release back to the production system which result in Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009relatively longer squeeze lifetimes and less inhibitor waste... Calcum chioride can be used as the precipitant and may be mixed with the inhibitor or introduced as pre-flush or after-flush solution. Calcium phosphonate or calcium polycarboxylate salt are sparingly soluble and their solubility decreases with increasing temperature and increasing pH. By pumping the inhibitor as a mildly acidic solution, the increasing temperature or higher pH in the reservoir acts to induce precipitation. SCALE REMOVAL In the oil production industry today, it Is possible to predict scale deposition in advance using ‘computer models. If these models were entirely accurate it can tell when and where scale would form,so scale inhibitor programs could be planned to suit each situation and mineral fouling would not be a problem. However, water composition, water cut, temperature and pressure can change unpredictably making it possible for conditions to develop that would allow a mineral scale to form within days and certainly before a preventative program can be put in place. Even then, other processes such as corrosion product fouling may still allow deposits to form. ‘As a result, chemical scale dissolvers have been developed that are claimed to be suitable for most common oilfield scales. These products range from simple acids to sequestrants and complex formulated product, Alternatives to chemical scale dissolvers are mechanical methods such as reaming and water jetting or the complete replacement of the fouled section. Non-chemical methods can be the only viable option for treating thicker and consolidated deposits. In general if the scale is accessible and thin enough to allow the dissolution reaction to proceed to completion then the use of chemicals is usually cost effective. In order to plan a scale removal treatment it is essential to have the maximum. information about the type, position and extent of the deposit. Chemistry of Scale Dissolvers The options available for treating calcium carbonate and barium / strontium / calcium sulphates are given as follows. Hydrochloric acid (HCl) Sulphamic acid (NH,S0;0H) Citric acid Formic acid (HCOOH) and Acetic acid (CH;COOH) Hydroxyacetic acid (Glycollic acid) ‘Sequestering Agents APPLICATION OF SCALE DISSOLVERS Successfull application of scale dissolver is critically dependant on the nature of the scale, its extent and its location. In surface equipment / lines it is normally possible to establish these facts and the treatment planned accordingly. Compatibility of the candidate cissolver with materials of construction and with dilution water must be established prior to the treatment. Recirculation of the dissolver through the scaled zone is the normal procedure using a heat exchanger if necessary to warm the solution, Treatment of scales in tubular or in the near well bore is less simple to plan due to the uncertainty of the extent or nature of each fouling deposit. The number of ‘failed’ treatments is a reflection of these difficulties and is probably associated with wrong choice of dissolver. If carbonates are indicated then treatment with 15% HCl or Musol - HCI solution, soaking is likely to improve fluid productivity. Alternatively, a less corrosive organic acid based product can be used with longer soak times. Copyright ® Hudson Technology & Strategic Studies, Ottawe-Canada 2009RADIOACTIVE SCALE Many reservoir brines, which are rich in barium, also contain trace levels of radium. Radium is radioactive and its sulphate has a lower solubility product than barium sulphate. Deposits containing significant radium are described as NORM (Naturally Occurring Radioactive Materials) or LSA (Low Specific Activity scale). Barium sulphate scale deposits frequently contain low concentrations of (co precipitated) radium sulphate. These low specific activity (LSA or NORM) scales are problematic as they can be sufficiently radioactive to be covered by regulation regarding their safe disposal. Mechanical methods of scale removal may result in the generation of toxic radioactive dust. It is advantageous if the scale deposit can be solubilised to enable disposal in solution (re-injection for example). EDTA and DTPA salts have been used successfully to reduce the risk of handling solid radioactive scale deposits on tubular goods. IDENTIFICATION OF MINERAL SCALES It is important that representative samples of the scale deposit are taken. Unfortunately there is no universal scale dissolver so itis only after sample analysis that an optimum treatment can be planned. Scale deposits can be laid down in layers and the composition of each layer can vary both in cross- section and laterally this information will help treatment design and may also provide an explanation as to how the deposit formed in the first place, The use of electron microscopy coupled with EDAX (Energy Dispersive X-ray analysis) enables an accurate map of the elemental composition to be obtained in sample cross-section. This is an ‘expensive analytical tool and much care is required in sample preparation. X-Ray dim-action techniques enable the mineral composition to be identified. Infra-red and other spectroscopic methods are sometimes used particularly if there is a significant organic content build up within the scales layers. ANALYSIS & SAMPLE ACQUISITION A normal ionic analysis should be made on the produced water through out the service life of any well. This should enable water composition trend review, allow accurate scale prediction modeling, squeeze ‘modeling and post squeeze assessment. Once a well has aut water, ion tracking on frequent basic is highly recommended. Regular 12- ions assay (cations and anions) plus pH and conductivity of the produced water from each well will provide the basis for interpretation of reservoir current status and expected future performance. For this reason it is essential to use analysis of other soluble fons (jon tracking) to provide an ‘early warning’ of scale inhibitor depletion. Fa Of key importance are ‘scaling’ ions such as Ca ** , , St ?* , HCOs and SO, , along with other anions and cations such as Na‘, K*, Mg”* and Fe 2*°*. Cations can typically be determined using Inductively Coupled Plasma Spectrometry (ICP) while HCO; and SO, can be determined using chromatography based techniques/wet chemistry. ‘Additionally the determination of volatile fatty acids is important and is best run at the same time as the bicarbonate determination. Historically bicarbonate has been determined by a titration based method of a fresh brine sample, but this method actually titrates part of the fatty acid present as well. This leads to overestimate of the bicarbonate present. Water analysis and residual inhibitor analysis using ion Chromatography offers significant benefits over conventional analytical techniques used to analyze oil field brine samples as the techniques utilized are unaffected by influences such as dissolved hydrocarbons and solution matrix matching, Produced Water Analysis Knowledge of the nature of any underlying aquifer or brine associated with oil or gas reserves is critical to the design of wells, pipelines and facilities, It is often difficult to obtain a representative sample of water since composition varies with location and depth. Water in the reservoir has associated gas with it that will be lost when a reservoir sample is taken to surface and the pressure reduced. In particular, the loss of CO; can affect the water chemistry. ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Ideally, downhole pressurized water samples should be taken from the water bearing formation and maintained at pressure until analyzed in the same manner as downhole pressurized oll samples, The issue of sample preservation is important for reliable monitoring of scale inhibitor residuals. Sampling Practices vary between operators however; it is recommends taking duplicate samples during the routine weekly or bimonthly sampling program, In order to determine the water chemistry, these should be sampled into clean one liter plastic containers, leaving no ullage space (to preserve any dissolved gas remaining at the sample location in solution. Changes in temperature during transportation can alter the solubility of dissolved salts in the brine and could lead to precipitation. If this occurs, then the analyses carried out remotely could underestimate the true ionic composition of the brine. Thus, it is recommended to take a series of brine samples in several sample containers stabilized differently to allow accurate laboratory results. Collection and testing of stabilized water samples In the first bottle, the brine is added to the sample container without any additives. In the second, the brine is sampled into a bottle which contains up to 5% HC which will preserve the calcium ions in solution by reducing the pH and increasing the solubility of calcium carbonate, The volume of HCI must be known accurately. In the third, the brine Is sampled into a 10% EDTA solution. As with the HCI, it Is important to know accurately the volume of sample and of EDTA solution in order to calculate the effective dilution. The EDTA preserves the barium and strontium ions in solution by chelating them. In the fourth, the brine is sampled into an accurately known volume (approximately 5 volume %) of a reducing acid such as erythorbic or acetic acid present at 5% concentration, this helps to preserve the Iran in solution. ‘Thus, it is recommended to determine the pH and the bicarbonate ion concentration at the sample location if possible. If the CO; levels in gas streams associated with this water are known, these should be reported at the same time. This data allows some scale prediction software to theoretically model the water chemistry to confirm the analyzed data, Gas Analysis Accurate knowledge of the typical gas analysis at selective locations of the process is equally important as the brine analysis. The partial pressure of CO; in the equllibrium that can result in CaCO, formation is of prime importance. The fractions of O, and H,S and the light hydrocarbons fractions are equally important, Accordingly, there must be a predefined gas sampling and analysis scheme that is strictly followed through out the life of the reservoir. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Paraffin/Wax deposition Formation and Characterization of Wax Deposits Effect of Asphaltene on Wax deposition Modeling / Prediction of Wax Formation Laboratory Characterization of Crude Oi! ‘Wax Deposition Inhibitor Chemicals Wax Control Treatments Wax treatment chemicals ‘Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘THE PROBLEM OF PARAFFIN/WAX DEPOSITION IN OIL FIELDS Crude oil contains paraffin and microcrystalline paraffin of varying chain length and complex molecules with aromatic properties as part of its hydrocarbon content. Crude oils are in equilibrium within the reservoir but as the hydrocarbon and aqueous fluids are produced, this equilibrium is disturbed and the solubility of the high molecular weight fractions is affected by the change in conditions. As a result of the equilibrium disturbance high molecular weight paraffin may deposit in the reservoir rock, in the tubular string, pumps, vessels and In flowiines. ‘The term ‘Wax’ or ‘paraffin wax’ describe those organic deposits that contain n-paraffin of carbon number >18 together with a minor proportions of branched and cyclic hydrocarbons. The deposition of ‘wax results from the reduced solubility of high molecular weight paraffin in the produced crude primarily due to temperature reduction. The consequences of inadequate control of wax deposition can be most serious in pipelines. Increased crude viscosity will cause pumping difficulties. In an extreme ‘ase, it would be quite possible to form a wax ‘candle’ several kilometers long should the flow of crude be stopped for an extended period, The pressure required to restart flow in such a line maybe in ‘excess of the maximum allowable pressure of the pipeline. FORMATION AND CHARACTERIZATION OF WAX DEPOSITS ‘The solubility of wax molecules in crude oll depends on the chemical composition of the crude, the pressure and the temperature. A drop in temperature can initiate the process of crystallization of the least soluble, highest molecular weight paraffin. The loss of light ends from the liquid phase of the crude oil causes a change in Paraffin solubility and increase the crude viscosity. It is generally accepted that straight n -, and branched chain hydrocarbons ranging from C18 chain length upward represent typical waxy material. n-paraffin give rise to well-defined needle shaped microcrystalline waxes, ‘orthorhombic or hexagonal in nature. When crude oi is transported in a pipeline and the pipewall temperature falls below the wax appearance point, homogeneous and heterogeneous wax crystallization can occur. Wax deposits on the pipe surface, increase the surface roughness of the pipewall leading to an increase in frictional Pressure drop and turbulent flow. It has been postulated that wax does not bond directly to metal but is actually held in place by the natural surface roughness. Wax layers also reduce the cross-sectional area of the pipe and throughput of the line. During any shutdown, the static ail contained within the pipe could cool below the pour point and high yield stresses may cause difficulties during lines re- commissioning. ‘There are two principal mechanisms by which wax deposition is thought to take place, namely molecular diffusion and shear dispersion. Molecular diffusion transports wax which is in. solution whereas shear dispersion transports precipitated, solid wax particles. EFFECT OF ASPHALTENE ON WAX DEPOSITION Although paraffin solubility is reduced by the presence of resins and asphaltene, a significant reduction iin wax deposition is observed for crude containing a high proportion of asphaltic components. This is, almost certainly due to the fact that asphalts exist as colloidal suspensions In crude oll and that the colloids interfere with the processes of paraffin crystallization. Crude olls that contain both high proportions of waxes and asphalts are less liable to suffer from wax deposition problems. MODELING / PREDICTION OF WAX FORMATION A number of models for describing wax formation have been published. Prediction of freezing behavior is difficult due to the large number of components (n-paraffin, isoparaffins, naphthenes and other aromatic and cyclic species) which can crystallize from crude oils. Although these thermodynamic modeling packages give estimates of the amounts of deposited wax under specified conditions it is more normal for these parameters to be also determined by experiment when specific field problems need to be solved, Wax Content Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009No standard (ASTM or API) for wax content exists and it is important that the selected method is specified whenever a figure is quoted. Alternatively, the wax content can be estimated from the ‘molecular weight distribution. Wax Deposition testing In wax deposition tests the hot crude is stirred to simulate fiow in a cooled vessel in which test ‘coupons are installed. The total weight of paraffin deposited on the test coupons is measure and the test repeated after the wax deposition inhibitor has been stirred into the hot crude. WAX DEPOSITION INHIBITOR CHEMICALS Polymers based on polyethylene and polyurethanes are used to modify wax crystals to reduce pour point temperature and to prevent wax deposition. Surfactants are also used to reduce wax deposition. ‘The inhibitors work by distorting the shape of the crystal depositions so reducing the rate of individual crystal growth. ‘The paraffin inhibitor has to be injected before the paraffins have crystallized and has to be injected continuously injected typically in concentrations of 100 to 1,000 ppm. at a rate determined by the crude flow rate to ensure a constant concentration in the system all the time. It is usually necessary to dean the flowline before treatment commences, as the inhibitor will not remove the wax already deposited at the pipe walls. For a subsea flowline it may be advantages to Inject the inhibitor downhole as increased flow is obtained in the production tubing compared to the flowline, The crude is also at a higher temperature and this improves the efficiency of the inhibitor allowing a lower dose rate. The inhibitors are polymeric materials and can gel at low temperature resulting in the blockage of delivery tubing and valves. This may present some complications if the inhibitor is delivered by umbilical to a subsea pipeline. WAX CONTROL TREATMENTS ‘There are several options available for removing waxy deposits or controlling their rate of formation, these include; © Mechanical cleaning (Pigging) ‘= Thermal Techniques (insulation, hot water, hot oil, etc) + Solvents treatment + Wax treatment Chemicals (Wax Inhibitor / Pour Point Depressants / Dispersants) Pigging Routine pigging of flowlines to remove wax layers is a very common option. Pigs are launched through the pipe and will mechanically scrape wax from the pipewall and redistribute it within the crude in front of the pig. Not all of the wax will be removed but a much thinner, smoother deposit will remain which results in reduced pipewall friction and hence reduced pressure drop across the line. The frequency of Pigging is normally determined empirically in the field. Such mechanical methods virtually guarantee that cleaning will be achieved but the processes can be expensive in time and labor costs. A combination of pigging and other preventative measures may be optimal. The volume and distribution of the wax depositions is not known with precision and there is thus a risk that, during travel, the pig may pack the pipeline with wax which may result in a blockage of the Pipeline. In such cases a hot water flush may be used to loosen the deposits prior to pigging ‘operation. Flush water temperatures required are about 80 °C. Paraffin removers are surface active agent which wet and soften the deposits and are added to the water to assist in loosening the deposits and reducing the risk of pig stuck, Thermal Techniques The most straightforward method to limit wax deposition Is to provide pipeline insulation to maintain Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009its body temperature. If the temperature can be maintained above the wax appearance temperature then no wax will form. Burying a pipe in sediments or soils will provide insulation. In practice, insulation alone would not totally resolve a paraffin problem. Hot-oiling is the most commonly used technique for paraffin treatment in on-shore pipelines, A portion of the crude product is heated to a temperature significantly above the wax crystallization point and this is circulated back to the main crude flow. In long transcontinental flowlines, crude oil heaters are placed at specific locations along the whole length of the pipeline to reheat crude oil before it reaches the wax appearance temperature. Solvents treatment If a line is totally blocked with wax then heat is the technique most likely to succeed. If the line is less than 50% blocked then remediation through the use of solvents has a chance to succeed although in severe situations more than one application may be needed. The application of solvents is therefore is Viable providing the fouling is not too severe. A wide range of potential Hydrocarbon including gasoline, condensate, toluene, xylene, naphthas, trichloroethylene and other halogenated products have historically been used. Removal of paraffin wax deposits in lines and vessels in the field involve filing the affected areas with the chosen solvent and static soaking for 6 -24 hours. Long lines could be treated by slowly pumping the solvent slug but this approach could be logistically difficult and involves considerable down-time. ‘The use of heat with a solvent will speed up the process of paraffin’s dissolution. Hot solvents dissolve ‘waxes faster than cold solvents and the energy requirement to improve the solvency power of solvents is far lower than the energy requirement for hot oiling. Agitation (recirculation) will also speed up dissolution. ‘WAX TREATMENT CHEMICALS Chemical additives that are used to modify flow characteristics of crude oil can be classified in terms of the function that they serve; ‘+ Wax Inhibitors (Crystal Modifiers) © Pour-Point Depressants '* Dispersants Chemically, polymer wax inhibitors and pour point depressants are similar and the functions of wax inhibition and pour point depression can usually both be achieved with the same product. Many workers describe these ‘inhibitors’ as flow improvers. WAX INHIBITORS (CRYSTAL MODIFIERS) ‘Crystal modifiers are polymeric or high molecular welght organic molecules with both straight chain hydrocarbon and polar groups within the same molecule. It is the interaction of polar groups on the side chains with the crude paraffin molecules that largely determines the effectiveness of the product. Wax aystal modifiers inhibit deposition by co-crystallizing with the wax crystals and so preventing the formation of structured lattices at the pipewall. Crystal modifiers will only slow down the processes of deposition and not completely stop the formation of wax crystals. Wax crystal modifiers are formulated in hydrocarbon solvents (usually aromatics) to aid rapid dispersion into the oil phase. Active polymer content is usually in range 5 - 15%, Surfactants are commonly added as co-additives. The product is injected on a continuous basis to achieve maximum benefit and should be added to the warm / hot crude at a temperature above the wax appearance point. Application levels between 100 - 1000 ppm of formulated product are typically used. The use of il-soluble solid wax inhibitor ‘sticks’ has been recommended for treatment of gas wells or crude oll wells were continuous treatment is not possible. Tt is essential that the additive is added to the oil at a temperature at which both the additive and the wax are completely in solution, le. In an amorphous state. As the composition of a given crude changes with time, a polymer selected on the basis of an earlier optimization programme may need to Copyright © Hudson Technology & Strategic Studles, Ottawa-Canada 2009be replaced. Pour-Point Depressants ‘The pour point is the lowest temperature at which the crude oil will low. Once below the pour point then the crude will not behave as a Newtonian fluid but as a Bingham type fluid. Such fluids require a high shear stress to initiate flow but once flow commences the fluid behaves as Newtonian fluid again, ‘Additives that depress the pour-point and improve the flow characteristics at low temperatures are described as Pour-Point Depressants, As pour-point depressants are believed to operate by nucleation and co-crystallization processes it is not surprising to find that they are chemically similar to crystal modifiers. These additives are polymers with n-alkyl chains (primary or side groups) and other polar groups. Pour-point depressants are added continuously to pipeline systems upstream of the location corresponding to the temperature at which wax first appears in the crude. Typical application rates are from 50 - 1000 mg/liter. Depression of pour point of between 10 and 20 deg C has been achieved in some crude lines. Pour-point depressants are field sensitive, so performance at one location is no Quide to performance elsewhere. Dispersants Wax dispersants probably function by adsorbtion and water wetting the surface of the pipe. They also will adsorb to growing wax crystals thereby reducing the tendency for them to stick together. The overall effect is to allow less accumulation of wax on the sidewall. A good dispersant formulation will also function to penetrate accumulated deposits of wax, adsorbing on individual particles and enabling them to move freely back into the surrounding crude stream. Wax dispersants may be dosed continuously for inhibitory effect or by batch treatment to achieve remedial benefits. Anionic surfactants, including olefin sulphonates, polyolesters and other powerful wetting agents are potential active ingredients of wax dispersants. Formulations may also contain primary wax inhibitors (10 -30% total active concentration). Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009ee Asphaltene Deposition Asphalt Deposition Asphaltene Dissolvers Asphaltene Inhibitors / Dispersants Asphaltine precipitation prediction Laboratory Testing of Asphaltene Inhibitors / Dispersants Fleld Application of Asphaltene Solvent Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009ASPHALTENE DEPOSITION Asphaltenes are a fraction of crude oil defined being insoluble in n-heptane but soluble in hot benzene, xylene or toluene as defined in API 134, They are colloidal dispersions in the crude similar to resins, though larger. The actual composition of asphaltene is not defined though they are generally considered to contain n-alkyl. “Asphalt” is the term used to describe the mixed precipitate of asphaltenes and resins. Asphalt is a tacky substance deposited by lower alkanes. The naturally occurring polar, polycydic hydrocarbon fractions of crude oil are known as asphaltenes and resins. The solubility and precipitation of these products is strongly dependent on crude composition, pressure and temperature. The operating problems caused by asphaits are similar to waxes but are in fact more difficult to predict and to mitigate, Some crude olls have no tendency to deposit asphalts whereas others are so severe that the whole economics of field development depends on proper deposition control. ‘Apart from the physical blocking processes that can occur in the tubular string or fouling problems at the topside due to asphalt precipitation its effect is much more damaging at the reservoir where it can ‘cause permanent production deciine. Under reservoir conditions the asphaltenes are stabilized by the associated resins and aromatics of similar molecular weight which act as peptizing agents effectively reducing the asphaltene flocculation tendency. The association of asphaltenes and resins are generally thought to be colloidally dispersed rather than a true solution. The colloidal suspensions are in electro kinetic balance, if the concentration of the resins falls below a critical value then asphaltene fouling can initiate as the electrical charge distribution is upset. The asphaltenes will precipitate until the resin/asphaltene balance is restored. Crude oils with a high ratio of resins to asphaltenes do not readily form deposits whereas if this ratio is low then flocculation and deposition is almost inevitable. ‘As asphaltenes are stabilized as colloidal particles, any actions of a chemical, electrical or mechanical nature that tends to disturb these particles will lead to flocculation and precipitation. Use of carbon dioxide for enhanced oil recovery can also cause destabilisation and asphaltene precipitation but this occurs in the reservoir and not in the pipeline. CO, appears to cause a reduction in solubility of asphaltenes (similar to lower alkanes) and in addition can cause rigid film formation at the aqueous Interface because of its effect on the pH of the aqueous phase. ‘Acidisation of a well following drilling completion to improve wells injectivity can result in the back flush of strong electrolytes as spent acids into the flowlines and this will cause precipitation. Other ‘acidic solutions, e.g. hydrochloric acid workover solutions, can also cause rigid film formation if asphaltenes are present. Changes in the crude composition can also result in destabilisation and precipitation. Asphaltenes are not generally a problem in pipelines which transport crude from several wells from the same reservoir as the fluids are in balance. Problems occur if crude oils from different reservoirs are co-mingled, as ‘occurs increasingly nowadays, the resin/asphaltene ration may be adversely affected. The effect of the co-mingling can be evaluated by comparison of the crude compositions before and after mixing. The alkane balance and the asphaltene/resin ratios are the main indicators. ASPHALTENE DISSOLVERS ‘Aromatics offer the best solvency characteristics for both asphaltenes and resins. The aromatic solvent 's believed to act as a stabilizing agent and so has the same function as naturally occurring resins. ‘Simple aromatics such as Toluene and Xylene have been shown to be generally effective and are relatively inexpensive but have handing disadvantages (Rash points 5 & 27°C respectively). Higher alkyl-substituted benzenes have higher flash points but lower solvency than xylene. A commercial solvent consisting mainly of mono and di-substituted methyl naphthalenes is five times more effective than xylene. Aromatic solvents can be added continuously to crude in order to reduce the asphaltene deposition rate. ASPHALTENE INHIBITORS / DISPERSANTS Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009‘An ‘inhibitor’ would stabilize the colloidal association, reduce the rate of particle flocculation and change the point of asphaltene flocculation onset. Many so called inhibitors are actually acting as dispersants, reducing the rate of agglomeration, reducing particle size and thus reducing deposition to surfaces. Alkyl-aryl sulphonic esters are common dispersants (e.g., didecylbenzene sulphonic acid, DDBSA), Laboratory evidence suggests application rates will be in excess of 1000 ppm. Continuous circulation of hot (deasphalted) oils can also reduce or eliminate the problem effectively by diluting the crude. ASPHALTINE PRECIPITATION PREDICTION Prediction of asphaltene deposition through laboratory experimentation is extremely difficult due to the problems of obtaining (and maintaining) live downhole crude samples at reservoir pressure and temperature. There are no complete predictive tools available that define the severity and position of asphaltene deposition. A thermodynamic modeling package is available that calculates flocculation conditions and the amount of asphaltene flocculated. Input data includes a PVT analysis and reservoir conditions, the amount of asphaltene, the resin/asphaltene ratio and one set of fiocculation conditions. LABORATORY TESTING OF ASPHALTENE INHIBITORS / DISPERSANTS: The asphaltene content is determined by a standard ASTM procedure and defined as that fraction of wax-free crude that is insoluble in n-heptane but soluble in hot benzene, xylene or toluene. A flocculation point test would be most suited to evaluation of potential inhibitors where as dispersancy is measured to evaluate asphaltene dispersants. The Asphaltene Flocculation Point is defined as the ‘onset of asphaltene flocculation, caused either by a PVT change, or by any other change that affects the crude oil composition. ‘The lower the pressure can be reduced to or the more n-pentane or n-heptane can be added to the crude oil before flocculation occurs, the more stable are the asphaltenes in the crude. An increase in the flocculation point correlates with an increase in asphaltene stability. The efficiency of asphaltene inhibitors can be assessed by comparing the flocculation point of an uninhibited crude oil with the result of a test performed with inhibited crude. FIELD APPLICATION OF ASPHALTENE SOLVENT “The success of any field treatment depends on a number of factors but it is crucial that the position of the deposit is known with some accuracy and that a reasonable estimate of the quantity of asphaltic deposition can be made. Compatibility of the solvent with elastomers and plastics materials that are contained within the system must be checked as swelling and/or embrittlement of elastomers are possible even after relatively short contact times.. Aromatic solvents and particularly condensed ‘aromatics are aggressive against many common elastomers, which are used in oilfield application as seals, gaskets etc. Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Gas Hydrates Formation Hydrate Formation Hydrate Plug Dissipation Prediction of Hydrate formation Hydrates control Chemical Inhibitors Hydrate Removal Copyright ® Hudson Technology & Strategic Studies, Ottawa-Caneda 2009GAS HYDRATES FORMATION IN OIL FIELDS Hydrates are a form of ice generated by the reaction of water with Low molecular weight hydrocarbon molecules. Low molecular weight hydrocarbon gases, in particular methane, ethane, propane and butane, can be solubllised by water under conditions of high pressure and low temperature to give crystalline dathrate-like solids known as gas hydrates. In a few Isolated situations hydrates may form in the absence of water such as those formed in 2 mixture of certain hydrocarbons and hydrogen sulfide. Solid natural gas hydrates can be a major problem as they can block transmission lines, plug blowout preventers, cause tubing and casing obstraction and foul heat exchangers and valves. Additional risks of hydrate formation occur when wells are shut-off, as the decrease in temperature coupled with the development of a gas cap increase the risk of hydrate formation. Natural Methane (CH, ) Hydrate is the most common form of a unique class of chemical compounds known as dathrates. Clathrates are characterized by a rigid, open network of bonded host molecules that enclose, without direct chemical bonding, appropriately sized guest molecules of another substance. Hydrate is the term commonly used for those clathrates in which the host molecule is water. Gas hydrate refers to hydrates in which the guest molecule is a gas. Hydrates can form as a simple consequence of temperature decline, which in turn can be the result of, local pressure drops due to turbulence or gas expansion. The occurrence of hydrates is most likely where pipelines are routed along the seabed for a considerable distance allowing the contents to cool below the critical hydrate forming temperature. HYDRATE FORMATION ‘The hydrates are generally formed at low temperature and high pressure and are often precipitated first at areas where there is a high turbulence associated with Joule-Thomson cooling, for example downstream of a valve or choke. Once the initial deposit of hydrates is formed the rate of increase of the hydrate deposit increases as the A P increases across the blockage leading to a lower local temperature and increased water condensation. The pipeline is eventually plugged and flow ceases. The domain of stability of the hydrates depends on the composition of the fluids, A hydrate curve for a pure hydrocarbon is schematically presented in the relevant slide. Where there is a mixture of hydrocarbones there is a family of curves so that the overall hydrate curve Is a blurred boundary. ABC is the curve for a system where water is the only liquid present in the pipeline and EBF is the freezing point of water. Line GCH is the dew point for the hydrocarbon phase. At point C, the four phases may be present: aqueous liquid, hydrocarbon liquid (HC), hydrate and vapor HYDRATE PLUG DISSIPATION To dissipate the hydrate, it is necessary to drop the pressure in the pipeline below the critical hydrate formation pressure for the ambient temperature. Both the upstream and downstream. pressures generally need to be reduced; otherwise the high pressure upstream fluids reform the hydrate as downstream section sublimes and allows flow. An alternative approach would be to warm the pipeline above the critical hydrate temperature for the operating pressure but this approach is not feasible for a submarine pipeline unless the pipeline has been installed with some form of heat tracing provision. When calculating the hydrate formation temperature the salinity of the water must be taken into ‘account. Increasing salinity lowers the temperature at which the hydrates form. However this effect Is only marked at high salinities and it is important that the effect is calculated allowing for the dilution that will occur as increasing water condenses, PREDICTION OF HYDRATE FORMATION Mathematical models have now been developed (HYSIM) which is based on phase equilibrium equations and include parameters for the common thermodynamic inhibitors, methanol, ethylene glycol and di and tri- ethylene glycols. When the gas composition, pressure and temperature are known then the occurrence of hydrates in the line can be predicted. HYDRATES CONTROL Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Formation of hydrates is prevented by maintaining the gas "dry". However nominally dry gas pipelines ‘can suffer hydrate formation if the gas flow rate is sufficiently high for the Joule-Thomson cooling to allow precipitation of water. The usual practice is to dry the gas to a dew point 5 -10° C below the lowest anticipated ambient temperature. To achieve a Dry gas, the wet gas product is passed through scrubbers containing triethylene glycol in order to remove water. Unfortunately this technology is not applicable to sub-sea wellhead completions or to small platforms with limited space, Removal of water (high thermal capacity) may increase the demand for insulation in places which does not intially required insulation. Pipe insulation is an important method for preventing or delaying hydrate formation. Pipelines that are insulated or buried will maintain higher fluid temperatures during normal flow coneitions. Regular chemical treatments for hydrate control offer the most cost effective option for the large majority of oil and gas fields. CHEMICAL INHIBITORS Hydrates are frequently controlled by the application of chemical inhibitors. There are two distinct types of inhibitor, the traditional thermodynamic types such as glycol and methanol and the so called threshold types’ or low-dose hydrate inhibitors (LDHI), including kinetic inhibitors and anti- agglomerators. Thermodynamic inhibitors act essentially as anti-freezes, permanently changing the solvation characteristics of water. Threshold inhibitors on the other hand reduce either the rate of hydrate nucleation or the rate of agglomeration of hydrate particles. HYDRATE REMOVAL Hydrate deposits in pipelines can be extremely difficult to remove, An increase in temperature or a decrease in pressure could solve the problem. Depressurization at each end of a plug within a pipe may siowly cause the hydrate to dissociate but the process is potentially risky. Ethylene glycol and methanol are used to remove existing hydrate deposits. Treatments would normally involve pumping a significant volume to the fouled area and allowing soaking for a few hours. Threshold inhibitors do not dissolve hydrates. The use of ammonium chloride plus sodium nitrite is strongly exothermic and is claimed as @ technique for dissolving hydrates and waxes. It is important to know that methanol has a damaging action being ‘a strong precipitant of wax. So in case of crude with potential was problems careful study of the possible effect of Methanol on wax shall not be overlooked, ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Oil Field Emulsion Formation of Stable Emulsions Emulsion Breaking Demulsifier Chemicals Demulsifier Selection Demulsifiers effecincy tests Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009EMULSION Turbulence in the downhole, at the wellhead, in the manifold or the transmission pipeline can cause intense mixing of the oil and water resulting In the formation of emulsion, Emulsion is a stable mixture of oll in water or water in oll where the minor phase persists as micro-droplets within the major phase. ‘Almost all oils will form an emulsion which does not necessarily persist. When a crude oil contains both natural emulsifiers and stabilizers and is mixed with sufficient energy input through turbulence, it can form stable emulsions with the produced water. These stable emulsions cause problems in separators, storage and will increase the pressure drop in the pipeline. FORMATION OF STABLE EMULSIONS In the crude oil/water system the natural emulsifiers and stabilizers indude, Asphaltenes, crude oil resins, porphyrin complexes, paraffin particles, clay and corrosion products. These substances contain polar groups such as carboxyl and phenol groups. Asphaltenes and porphyrin complexes have the ‘most influence on the emulsion process and on emulsion stability. They act by altering the surface tension between the oil and the water droplets and also semi-dissolve in the water forming films around the micro-droplets which prevents them from coalescing. Paraffin particles and to a lesser ‘extent clay and sand tend to stabilize the emulsion once it is formed. ‘The emulsifiers and stabilizers are compounds which often incorporate a hydrocarbon tall with an active soluble head. Asphaltenes and resins have fatty acid or alcohol heads. Water droplets are spherical because of Its surface tension characteristics. The water droplets fail to coalesce because they are encircled by a hydrocarbon layer preventing water-to-water contact. To remove the water from the emulsion, it is necessary to both overcome the charge difference between two particles so that they can meet and merge, while at the same time disrupt the encircling hydrocarbon film to allow water coalescence. The demulsifier chemicals must be both hydrophobic and hydrophilic to interact with both oil ad water and later surface charges and interfacial tension. Relevant Variables The composition of the produced water has a significant effect on the formation and stability of the emulsion. High salinity reduce emulsion tendencies but calcium and magnesium ions react with organic acids in the crude ail (e.g. napthenic acid) to form surfactant materials which stabilize the emulsions. Bicarbonate ions in combination with calcum and magnesium also act to stabilize emulsion. EMULSION BREAKING To remove the water from the oil it is necessary to cause the water micro droplets to coalesce sufficiently to form bigger droplets which should settle by gravity as a separate phase form the oil. The rate of settlement of the droplets depends on the size of the droplet. The volume of the droplet is a major factor as its effect on separation rate is a square of the droplet radius. Reducing viscosity will also have an effect and heating the crude is a common method of increasing the rate of water shedding. Heating alone would be too slow for normal crude ail field requirements. A demulsifier chemical is usually required to break the emulsion and enhance phase separation. The demulsifiers are added as early in the production process as possible as aged emulsions are more difficult to break as the emulsion stabilizers will have concentrated at the emulsion oil interface. DEMULSIFIER CHEMICALS. The demulsifiers are surface active chemical which reduce the charge on the interface allowing the droplets to coalesce. It is usually necessary to gently agitate the emulsion to encourage micro-droplets to meet but continued intensive mixing can result in re-emulsification. Demulsifiers are added to the emulsified oll and act to reduce the stability of the interfacial films which prevent coalescence. Dosage rates for demulsifiers vary from 1 to 10 ppm. The demulsifier is injected into the manifold and effective demulsification in the flowlines results in a reduction in pressure drop. The chemical formulations are termed demulsifiers if they break water-in-oil emulsions. Chemicals that Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009break oil-in-water emulsions are termed reverse demulsifiers, DEMULSIFIER SELECTION To enable the supplier to propose suitable chemicals, the following basic details shall be ‘communicated: Type of crude oil, API, acidic components, paraffine and asphaltene content. Expected turbulence within the flowline and the residence time, flowline temperature. Produced water composition: bicarbonate, calcium, magnesium concentrations, TDS. Nature of the eventual dehydration plant. Residual water content (BS&W), salt content, allowable oil in discharge water. Location of injection. DEMULSIFIERS EFFECINCY TESTS It is usual to test proposed chemicals using the bottle test technique. These are simple tests in which crude cil and water are stirred/agitated and the demulsifier is added once the emulsion is formed. The amount of water separated Is measured at given intervals of time. The demulsifier is tested to find the minimum concentration needed and also to ensure that it has no adverse side effects. Overdosing of demulsifier must usually be avoided to prevent formation of a reverse emulsion. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Chapter 8 Integrity Management Systems ‘Subsea pipelines, Risers and Subsea equipment + Design consideration & Material selection ‘+ Cathodic Protection + Coating & Lining + Monitoring & Inspection * Corrosion Control Measures * Chemical Treatment * Chemical Injection Facilities Offshore Structures ‘+ Design consideration & Material selection + Cathodic Protection * Coating & Lining * Monitoring & Inspection Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009SUBSEA PIPELINES, RISERS AND SUBSEA EQUIPMENT Design consideration & Material selection + Pipeline design, construction, lying, testing shall be in accordance with DNV OS-F101. = A corrosion allowance of 3 mm is generally recommended for carbon steel piping, unless higher corrosion allowance is recommended by the specific project design philosophy. * Corrosion resistant alloy CRA's or cladding may be considered provided that selection is justified and supported through appropriate life cycle cost analysis. + No corrosion allowance shall be considered for pipelines handling dry gas or non corrosive fluid. A gas is considered dry when the water dew point at the actual operating pressure is at least 10 °C lower than the operating temperature of the system. * All pipelines, risers, associated pipework and fittings in contact with produced fluids shall be ‘manufactured from materials specified for sour service in accordance with NACE guideline for ‘sour Services application NACE MR-0175. = Subject to life cost analysis, flexible pipelines might be considered for effluent, injection or disposal water handling. = Electrolysis nickel plating on carbon steel valve trim is not acceptable. + Door dosure mechanism for pig traps shall be overlaid with (INCONEL) on their sealing face to avoid corrosion induced leakage. = Subsea tie-ins can not regularly be cleaned and dewatered by pigging, limit the intelligent Pigging operation to speafic techniques, reduce the efficiency of the corrosion inhibitors and create area of stagnant fluid in places. Accordingly, all new Cil, Gas and Water lines should be designed without subsea tie-ins. ‘+ Pipelines design shall ensure a minimum flow velocity of 1 m/s. * Gas pipelines shall be internally dean prior to construction by open grit blasting using inert grits such as garnet or equivalent, to ISO 8501-1 level 2%. Such internal cleaning may be waived for water and oil pipelines. + For submerged application, where dissolution of a thick zinc layer may cause loss of bolt pre- tension, phosphating may be used. + The use of poly-tetra-flouro-ethylene PTFE coated bolts, nuts ans washers may also be used provided electrical continuity 1s verified. Cadmium plating shall not be used for subsea applications under any circumstances. To enable on-line pigging with minimum interruption to operation new lines of the same size may be equipped with topside connection (Cluster design) which may allow pigging more ‘than one line at a time. * Main transmission oil and gas pipelines shall be provided with permanent launchers and receivers to enable inspection using conventional intelligent pigging tools (MFL or UT). = All infield new pipelines shall be equipped with provision for temporary facilities to allow routine cleaning and intelligent pigging operations. Where space limitation is a constrain, consideration should be given to installation of vertical launcher and receiver Any pipeline with a length fess than 2 kilometres shall not be equipped with launcher / receiver facilities for economical reasons. + The pipeline design and installation shall permit the intelligent pig to be run through the complete pipeline from one end to another in one pass avoiding the need for multiple stage ‘or both side runs. In additional, the detailed design requirements of the pipeline shall allow ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Unrestricted passage of the pigs. The design of the handling facilities at the launching and receiving ends should cater for the maximum train length of pigging tools available and enable safe and easy handling of the pig during launch and receive. Consultation with leading intelligent pigging tools shall be established to identify the suitable Launchers/Receivers length, Cathodic Protection "The design life of the Cathodic protection systems is 40 years. The system should be designed to DNV RP B401 code using bracelet sacrificial anodes, made of aluminium alloy, Galvalum IIT or equivalent. The onshore and subsea section of pipelines shall be electrically isolated by either insulating joint or insulating flange kit. Insulation kits shall be annually tested in accordance with the requirements of the company specification, ‘Anodes sleds/rafts shall not be used in lieu of retrofitting bracelets or stand -off anodes for the infield lines and offshore structures unless there are good technical justifications endorsed by the appropriate technical authorities for such replacement. Coating & Lining * Subsea lines shall be protected externally using Coal tar enamel or three layers Polypropylene/Polyethyiene coating in accordance with the company specification. 1 Concrete weight coating applied for bouncy control shall be completed in accordance to the : requirement of the company specification. Field joints shall be protected by a combination of ' @ polyolefin-backed wrapping system or PVC tape . Subject to fire risk assessment, risers and associated piping may require passive fire protection coatings (In tumescent fireproofing). Risers shall be protected with a Polychloroprene (Neoprene) coating in the submerged and splash zones. Riser clamps shall be lined with Polychloroprene and be integrated into the jacket cathodic protection system. Monitoring & Inspection * The Integrity authorities shall develop a solid strategy for intelligent pigging of infield Pipelines based of sound operational and business risks, Many infield pipelines are not readily accessible for intelligent pigging inspection and some indude subsea tie-ins. Evaluation of the condition of these pipelines can rely on topside | corrosion monitoring, fluid analyses, spot ultrasonic and corrosion prediction modelling. Remnant Life Assessment (RLA) based on an adequate intelligent pigging data may enable establishing remaining life for other lines falls under the same service conditions. To minimize operation interruption for reasons related to routine pigging operations, lines of the same size operated in series may be provided with only one launcher/receiver at the start and end of the segment so more than one line can be pigged together through one launch (Clusters concept). Periodic potential surveys of the pipelines shall be made at 5 years intervals to ensure that the cathodic protection potentials are adequate. Al pipelines at field's periphery shall be fitted with appropriate side streams to enable proper sampling of fluids, allow chemical treatment evaluation, and accommodate enough number of bio-probes for proper sessile bacteria measurement. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Corrosion Control Measures ‘Chemical Treatment ‘The corrosion control strategy for the infield pipelines is to keep the pipelines clean by routine pigging using polyurethane foam and steel body Bi-directional pigs to improve the effectiveness of the chemical treatment regimes, remove corrosion products, debris and ‘organic deposits, displace accumulated water and to scrape and remove microbial bio-flm. A procedure shall be developed for the cleaning and drying of the pipelines following hydro- testing. For gas pipelines such procedure should include a provision to remove salt deposits (Chlorides) formed during hydro-testing and dewatering. Pipelines planed not for use for prolonged periods may suffer extensive internal corrosion and these shall be mothballed, prepared for shut in by dosing with multipurpose corrosion Protection chemical (Corrosion Inhibitor, Biocide and oxygen scavenger blend). Infield water injection lines not equipped with launching and receiving facilities shall be mechanically cleaned once every 3 years, preferably at shorter intervals. Other pipelines Provided with adequate | provision shall be pigged once every 3 months. In all new pipelines, riser damps and flanges shall be positioned at the highest point of the offshore structure as far as practically possible from the splash zone. As part of the preparedness of the company to cater for possible pipelines leak due to corrosion or third parties interventions, a complete set of damps and mechanical connectors shall be made available and kept in good condition all the time. All crude oil lines shall be treated with corrosion used for different crude oil and gas lines. ibitor. Different types of inhibitors shall be As a general rules, Corrosion Inhibitors shall be injected at 5 ppm for infield and main crude ail transmission lines. Wet gas lines are protected on the basis of 0.5 liters/mmscf. Dry gas lines are protected at 0.25 liters/mmscf. Following routine or intelligent pigging operations the corrosion inhibitor injection dosage shall be increased 4 times the routine dosage for 24-48 hours to establish a new film on the pipewalls. Residual inhibitor shall always be evaluated after deaning pig runs. The corrosion inhibitors injection rate should be routinely adjusted to match product flow rates so that the correct dosage is achieved. Injection of inhibitor into dry gas streams is not generally required except when lines are shut-in for prolonged period and/or there is concern that water wet products could enter the pipeline. Particular care is necessary to ensure that the right inhibitor solvent package is used (preferably hydrocarbon base) to minimize the risk of gunk formation in the system. Scale inhibitor shall be used in the water injection system to prevent scale formation in the de-aeration columns, pipelines and subsurface equipment. ‘Acid treatments to improve injectivity of water injection wells may be used for carbonate scale removal at the formation face. Corrosion inhibitors shall be selected after independent laboratory testing of candidate formulations. Chemicals supply contracts shall be technically reviewed every five years to ensure that most cost effective formulations are being used and to cater for change in crude and brine composition. Field trials may be required to ensure product effectiveness under operation condition and to optimize the injection dosage. Carry out necessary QA/QC checks to ensure that all chemicals delivered to the company are Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009in full compliance with the approved products and they are effective to achieve the required function. Chemical Injection Facilities * Oil and gas flowlines shall be equipped with corrosion inhibitor injection facilities suitably sized to displace the required quantities of corrasion inhibitor to protect the risers, pipelines and topside equipment. Many wellhead towers do not have a gas source to operate gas driven pumps and in such ‘cases, the provision of a solar energy operated skid shall be considered. For new projects, supplied chemical skids shall conform to the requirements of the company and are designed similar to the existing skids, All chemical injection skids shall be provided with filling hatches with screed caps to enable corrosion inhibitor filling via typical gas station filling pumps directly from the chemical supply vessel, so chemical drums handling is eliminated. PROCESS EQUIPMENT, PIPEWORK, STORAGE AND EXPORT FACILITIES Design consideration & Material selection = A 40-year service life shall be considered for all installations and the minimum corrosion allowance provided shall be 3 mm, higher internal corrosion allowance may be specified as determined by the corrosion evaluation and risk assessment process. = Carbon steel is the preferred material unless corrosion rates are excessive. Solid corrosion resistant alloys CRA's or CRA's cladding should be used for vessels and tanks exposed to harsh environment where carbon steel prove to be inadequate. Materials selection for process faclties shall be decided through corrosion evaluation and corrosion risk cost benefit assessment process. All vessels, tanks, towers and pressure containments shall be delivered to the company with the base line inspection data completed by the manufacturer/supplier in accordance with the company specification, + Corrosion resistant alloys, non-metallic materials or cement lined carbon steel should be used for raw seawater handling. + All materials in contact with produced crude shall be resistant to sulphide stress cracking and hydrogen induced cracking in accordance with the company specification, The minimum grade of stainless steel employed for any application shall be type 316 in solution annealed condition. Stainless steel 316 L grades shall be specified for welded components. All welded component shall be selected and used in accordance with the company guidelines and specifications. = Instrument process fluid and impulse tubing shall be type 316L with 2 2 mm black Polyvinylchloride sheath or higher alloys depending on service. Bourdon gauge components shall be In a material resistant to stress corrosion cracking. = Good engineering practices shall be applied to ensure that corrosion problems created by oor design are eliminated elther on the existing installations or new facilities, this indudes:— © Dead legs. © Metal /Metal contact at support to pipes, vessels, tanks, structures, risers and any other process equipment. Riser clamps, boat landing and other critical equipments at the splash zone, Copyright © Hudson Technology & Strategic Studies, Ottawe-Canada 2009© Unnecessary Insulation. ‘© Redundant equipments and auxiliaries, "Consideration should be given to the use of non-metallic materials for items such as drain lines, small chemical tanks, vessels and pipework, Non-metallic materials shall have self- extinguishing properties and low smoke emission. "Bolts & nuts should be spun hot-dipped galvanized to the company Specification and with reference to ASTM A 153. = Reinforced Thermosetting Resin pipes (RTRP) may be used in lieu of carbon steel or cement lined carbon steel wherever there is a proven techno-economical merits. ‘Where space limitation does not allow RTRP use exclusively, hybrid installation may be considered where RTRP can be considered for straight runs and carbon steel or CRA materials for complex piping, fittings and valves. Particular attention and competency throughout design construction & installation phases must be observed. Cathodic Protection * Sacrificial anodes may be required to be fitted to the internal surface of vessels, tanks and other closed spaces such as the caisson legs at barges whenever requited as per the company specification. Designer should ensure that anodes are positioned in the aqueous phase. + Current Potential measurements and rectifiers output adjustment shall be completed on a monthly basis and any anomalies which may affect system performance shall be Immediately flagged and corrective measures executed. = Tank farms and other land areas where complex metallic structures and pipework exists, shall be protected using deep well impressed current ground bed. Inspection and Monitoring + Wall thickness measurements shall be made on vessels, tank, towers and piping systems at designated locations selected to be representative of the areas where damage mechanism (Corrosion, Erosion, MIC, etc) is considered most likely. Radiography shall be used for the inspection of welded small-bore fittings and nozzles. + All pressure vessels shall be inspected and endorsed according to the company inspection guidelines following a unified and documented generic Written Scheme of Examination for ‘each group of plant and equipment. + The injection water quality data shall be reviewed on a daily basis and the compliance with specification is routinely measured or otherwise flagged to the operation authorities and documented as part of the bi-annual water quality management report. + Water and oil samples shall be periodically collected from the hot oil system to ensure compliance with the system operating requirements with regard to water content, TDS and pH. ‘= Injection seawater breakthrough and dilution of formation water may also allow growth and activity of sulphate-reducing bacteria and result in reservoir souring. Side streams with Bio ‘Studs, Bio Probes or coupons shall be installed when needed throughout the water distribution system ideally at the terminal wells. = At major overhaul, SLOFEC inspection technique shall be conducted for tank floor without Temoving the floor lining. On stream Acoustic Emission inspections shall be conducted on 5 year frequency. Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Corrosion Control Measures ‘The design should avoid the condensation of aggressive fluids, galvanic coupling and prevent corrosion traps formed by un-drained water connections. Pipework shall be designed to permit free drainage thought out the entire system. Dead legs on pipework shall be eliminated where possible and in no case shall exceed three times the pipe nominal diameter. Pipe support columns should be provided with inspection windows or be hermetically sealed, Coupling of dissimitar materials should be avoided and where unavoidable, dissimilar metals, shall be electrically separated with an electrical insulator. Periodic removal of the scale deposits is recommended on heat exchangers and similar equipment, In situ Chemical cleaning techniques using environmentally friendly chemicals is recommended in lieu of mechanical cleaning. To protect flange faces, bolts and nuts against atmospheric and crevice corrosion and to ensure long term serviceability, wax impregnated cloth or elastomeric tapes and paste ‘complemented where applicable with non metallic protective bolts & nuts caps shall be considered for all flanged arrangements Pre-coating of the sted! and correct weatherproofing of pipework and equipment insulation shall control corrosion under insulation (CUI). Thermal insulation should be avoided unless it is operationally necessary or required for safety reasons. Areas of water ingress as identified by Thermography shall be further X-ray inspected to identify possible corrosion damage to the metallic body of vessels and pipelines. Al insulated plants and equipments shall be inspected every three years using Thermography techniques to identify areas of damaged insulation and possible water ingress. The survey results shall be the basic foundation to develop the insulation repair plan. Consideration can be given to new generation of elastomeric insulation systems in lieu of the traditionally used polyurethane foam and metallic jackets. Mothballing of facilities or pipelines shall be carried out using nitrogen gas, powder corrosion inhibitor or by cleaning & drying in accordance with the company specification. The effectiveness of the mothballing procedures shall be measured and assessed on an annual basis. Pipe supports shall be designed to eliminate crevice corrosion by means of continuously welded doublers plates, welded inverted T or pipe shoes. For existing facilities where mechanical intervention is not feasible, non-metallic barrier applied as a tape or a sleeve firmly bonded to the substrate shall be used to eliminate metallic contact between the pipe and the metallic support while providing adequate protection to the pipe. To reduce the risk of gas hydrate formation while minimizing the use of methanol, the gas dew point shall be maintained at a maximum (-9° C) in the summer season and at (-5°C) during the winter season, Chemical treatment To enable microbiological control at modules, hypochlorite solution shall be added at the upstream of the water injection sand filters to ensure continuous chlorine level at 0.2 - 0.5 ppm all the time. ‘The effectiveness of oxygen scavenger must be determined by continuous measuring the dissolved oxygen content of the water downstream of the vacuum towers by online oxygen analyzers. Proprietary dissolved oxygen analysis kits should be used as confirmatory test of oxygen content of the water. Biocides shall be used to prevent growth of microbial bacteria in particular sulphate-Reducing Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Bacteria (SRB) in the water injection systems. Biocide selection shall be reviewed regularly as part of the five-year water treatment chemical package eveluation scheme. Candidate biocide regimes shall be screened by laboratory testing, followed by extensive field trials. The use of environmentally friendly biocides such as HTPS is highly recommended in lieu of formaldehyde base biocides, OFFSHORE STRUCTURES Design consideration & Material selection Carbon manganese steel! Is the preferred materials of construction for all facilities wherever it is technically feasible. ‘The metal wall thickness of all primary structural members shall be provided with 10 mm corrosion allowance at the splash zone, which is defined as -1m to +5m above the MSL. Corrosion allowance is not required for structural members in the submerged zone, Handrails, gratings and vertical ladders shall be hot-dipped galvanized to ISO 1461 grade or thermal sprayed aluminium as indicated in NACE RP-0176. Composite (non-metallic) materials should be used where proven to be economically advantageous. Cable trays, cable ladders, sun shades, electrical enclosures, control panels, life rafts and boats are typical applications in the oll and gas production business. Non- metallic materials shall have self-extinguishing properties and iow smoke emission. Bolts and nuts for submersible application shall have a maximum hardness of 300 Vickers hardness number (10 kg load). ‘The boat fenders shall be tubular steel frame lined on the boat approach side with rubber fenders. Cathodic Protection Design of new and replacement cathodic protection systems shall be in accordance with DNV RP B401. The boat fenders assembly shall have separate cathodic protection systems designed in accordance with DNV RP B 401. Subject to analysis of the cathodic protection potentials of flowlines, super complexes and wellhead towers, retrofitting of the cathodic protection systems may be achieved by the attachment of anode rafts to the unprotected offshore faclities or by direct attachment of anode bracelet or stand-off anodes to pipelines and structures respectively. The submersed installation including Tanker Berths, Single Point Mooring (SPM) and sheet piles at the harbour shall be protected jointly by suitable coatings application and sacrificial anodes, Coating & Lining The practical service life of splash zone coatings is much shorter than the atmospheric zone, accordingly, the maintenance and major industrial repaint plans shall distinguish between the ‘two zones and each should have its own maintenance scheme, ‘The Maximum interval for industrial repainting is 15 years for all offshore and onshore installations at the aerial zones. Submerged and splash zones areas may be treated at shorter time span. Bolts and nuts in the aerial dry zone shall be spun galvanized to ASTM 123. Galvanized bolts shall not be used at the splash or submersible zones. All submersible bolts Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009and nuts shall PTFE coated. All clamps, pipe hangers and other pipe attachments shall be coated externally as per the company approved coating specification and internally lined with Polychlorprene (Vulcanized rubber) with @ minimum thickness of 6 mm, Colour coding of plant, services and helidecks marking shall be in accordance with the colour coding specification of the painting manual. Monitoring & Inspection ‘The integrity of the external coatings shall be assessed every 5 years as part of the Paint Audit pian, and at the end of the guarantee period (5 years guarantee bond) for new installations or industrial repainting programs. Offshore structures with Caisson legs shall be routinely inspected and condition monitored with particular attention to the level of generated hydrogen gas. The pH level, SRB and hydrogen gas concentration shall be routinely measured in an annual basis. Measurement of Cathodic Protection potentials of the offshore installation shall be carried out every five years as part of the Remote Operated Vehicles (ROV) survey. Structural integrity of all offshore structures shall be closely assessed under the requirements Of the Structural Integrity Management System SIMS. All anomalies generated out of the different inspection schemes shall be reported and necessary recommendation translated into appropriate work order into the CMMS system. Structures and facilities identifies to be at high risk (Rank 1), shall be included in the company master risk register. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Chapter 9 INTEGRITY MANAGEMENT OF DOWNHOLE FACILITIES Design consideration & Material selection Monitoring & Inspection Corrosion Control Measures ‘Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Design consideration & Material selection = Casing and tubing shall be fabricated from carbon manganese steels in accordance with the company specification. All Wells suffering CO, corrosion with a brine chloride level less than 120,000 mg/litters shall be completed using 13 % Chrome. Other wells with a chioride level from 120,000 up to 180,000 mg/Litre shall be completed with 13 % Super chrome. = Highly corrosive H,S gas wells shall be completed using corrosion resistant alloy (Incology 825) (UMSNO8825) in accordance with the company specification in such cases no corrosion inhibition is required. ‘+ The aquifer zone in Water injection wells historically operated as dump flood wells shall be sealed tight using appropriate liner to cover the entire aquifer zone. Monitoring & Inspection + All recovered Downhole tubing shall be marked, numbered and inspected on the Rig. ‘Additional, thorough inspection may be completed afterword at the driling yard on land. ‘The inspection data shall be used to verify the topside corrosion monitoring measurements. and to identify if problematic corrosion, mineral scale, Paraffin’s or Asphaltine problems are occurring. + Wells at higher risk of corrosion or with anticipated flow assurance problems shall be continuously monitored & assessed via Calliper/ Micro-Vertilogs surveys. Appropriate plan shall be developed to reflect the inspection scheme. ‘* Downhole weight loss corrosion coupons are a cost effective alternative to direct inspection and monitoring of Downhole corrosion and shall be used in selective wells to reflect Downhole corrosion rate where appropriate. = Topside facilities corrosion monitoring elements measurements (Weight loss coupons, linear polarization probes and Electrical resistance elements) shall be consulted and readings assessed to provide information on downhole corrosion behaviour. * A computer-based model for prediction of Downhole Corrosion shall be utilized to predict accurately the corrosion rate of individual wells under various operating scenarios once every two years and the outcomes documented in the annual assets corrosion report. "Downhole Scale, Paraffin’s/Wax and Asphaltine precipitation tendencies shall be modelled for all reservoirs, production streams and individual wells using appropriate software application, typically every two years or as deemed appropriate. * Representative fluid and gas samples shall be collected at critical locations at agreed frequencies. Samples collection, stabilization and testing shall be in accordance with the requirements of API 45 “Recommended practices for analysis of oilfield water”. Wells shall be sampled during routine well testing at a typical frequency of once every 6 Months for problematic wells and every two years for other wells. Al data generated out of the downhole tubing inspection, fluid sample analysis, downhole corrosion logs and probes, corrosion and scale prediction modelling and any other dat felated to Downhole corrosion and fiow assurance shall be archived on the shared folder created at the company intranet, il wells identified with noticeable seawater breakthrough or appreciated reduction of the produced water salinity shall be closely monitored and frequentiy assessed. The external condition of conductors protective coating shall be assessed as part of the Paint Audit Report, assessment shall also include ultrasonic wall! thickness and cathodic protection potential measurements. ‘Copyright © Hudson Technology & Strategie Studies, Ottawa-Canada 2009Corrosion Control Measures » All non-flowing wells (Planned and not planned for workover) shall be protected by tubing displacement (bull headed) via injection of inhibited diesel solution (90% diesel and 10% corrosion inhibitor) once every two year. "Necessary testing and screening of downhole corrosion, scale, Wax and Asphaltine inhibition/control/removal chemicals shall be completed by competent third party laboratories and successful chemicals identified and stocked to enable timely intervention where needs arise, "All chemicals intended for use for Downhole treatment shall be tested to ensure its compatibility with different brines and other chemicals used at topsides treatment. Necessary core flood testing and thermal stability shall be completed before any intended use for subsurface or reservoir treatment. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Cost of corrosion Engineering Best-Practice Corrosion Management and cost saving Why Is the cost of corrosion is high Corrosion Market Size Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009COST OF CORROSION The U.S. Federal Highway Administration (FHWA) released a break-through 2-year study in 2002 on the direct costs associated with metallic corrosion in nearly every U.S. industry sector. Initiated by NACE Intemational and mandated by the U.S. Congress in 1999, the study provides current cost ‘estimates for the time and identifies national strategies to minimize the impact of corrosion. “The study, entitied “Corrosion Costs and Preventive Strategies in the United States,” was conducted from 1999 to 2001 by CC Technologies Laboratories, Inc. with support from the FHWA and NACE. Its main activities included determining the cost of corrosion control methods and services, determining the economic impact of corrosion for specific industry sectors, extrapolating individual sector costs to a national total corrosion cost, assessing barriers to effective implementation of optimized corrosion control practices, and developing Implementation strategies and cost-saving recommendations. Earlier landmark study was conducted by Battelle Memorial Institute for the National Bureau of ‘Standards (NBS) currently, The National Institute of Science and Technology in 1976 and updated in 1995, The results of the original study were summarized in the report entitled, "Economic Effects of Metallic Corrosion in the United States". According to this study, the annual cost of metallic corrosion is estimated to be about 4.2 percent of the Gross National Product. Projecting this percentage to recent GNP information, this amount is about $350 billion annually. Furthermore, according to the study, $139 billion (40 %) of these costs could be avoided through application of existing technologies and best know practices. Although, there are some difference on the estimated annual cost of corrosion between both studies $ 276 Billions for the U.S. Federal Highway Administration (FHWA) compared to $ 350 Billions for the National Institute of Science and Technology there is general common understanding of the consequences and the mitigation measures. The bottom line is that the use of appropriate corrosion prevention and control methods protects public safety, prevents damage to property and the environment, and saves billions of dollars in the US. and worldwide. The aging infrastructure Is one of the most serious problems faced by society today. In past decades, corrosion professionals focused primarily on new construction specifying materials and designing corrosion prevention and control systems for buildings, bridges, roads, plants, pipelines, tanks, and other key elements of the infrastructure. Today, as much of the aging infrastructure reaches the end ofits designed lifetime, the emphasis is on maintaining and extending the life of these valuable assets. ENGINEERING BEST-PRACTICE Public safety concems have driven new regulations and corrosion control practices for gas and liquid transmission pipelines over the past few years, following 2 number of high-profile pipeline failures. Data management, system quantification through the use of global positioning systems, remote monitoring, and electronic equipment documents have significantly improved several areas of pipeline corrosion maintenance. The newest developments center on risk assessment strategies and pipeline Integrity management programs. ‘The study has determined that major cost savings can be realized by developing an optimum approach that includes both pipeline inspection and corrosion prevention strategies. Inspection strategies should include in-line inspection, hydrostatic testing, and direct assessment all currently available methodologies depending on the pipeline conditions. By developing new and improved inspection techniques and corrosion prediction models, corrosion professionals will be able to determine inspection intervals more accurately, prioritize the most effective corrosion prevention strategies, and, ultimately, increase the lifetime of the nation’s pipelines, ensuring safe and cost-effective transport of valuable energy sources. CORROSION MANAGEMENT AND COST SAVING The study clearly reveals that, while technological advancements have provided many new ways to Prevent corrosion, better corrosion management can be achieved using preventive strategles In non- technical and technical areas. These strategies are identified as follows: + Increase awareness of significant corrosion costs and potential cost savings. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Change the misconception that nothing can be done about corrosion. Change policies, regulations, standards, and management practices to increase corrosion cost savings through sound corrosion management. Improve education and training of staff in the recognition of corrosion control. Implement advanced design practices for better corrosion management, Develop advanced life-prediction and performance-assessment methods. Improve corrosion technology through research, development, and implementation. The costs of corrosion come in the form of either premature deterioration or failure resulting in the need for maintenance, repair and replacement of damaged equipment. Other sources of costs come from lost production and increased downtime of equipment arising from corrosion problems. In some ‘cases, corrosion cost also includes additional standby capacity that needs to be instituted to alleviate downtime problems associated with corrosion failures or unscheduled maintenance. According to the NBS study, a major portion of these expenditures could be eliminated using existing technology through application of best available practices. WHY IS THE COST OF CORROSION IS HIGH ‘One major reason for the high cost of corrosion is that the marketplace for corrosion products and services is very fragmented. It consists of many smaller companies that provide only a limited number ‘of services or products. This has made it difficult to develop consistent broad reaching approaches to solving major corrosion problems that truly include best available practices. Therefore, one of the major limitations resulting from the fragmented nature of the corrosion industry is the difficulty in the dissemination and utilization of information on best practices. It has also made it difficult to access many of suppliers of corrosion control technologies. For the same reason the concept of corrosion management has evolved to produce a process to integrate all parts the corrosion picture together so, a true picture is assembled and full and comprehensive review and assessment can be achieved. CORROSION MARKET SIZE Using the magnitude of corrosion expenditures by the corrosion technology categories given in the above mentioned survey leads to an estimate of the corrosion expenditures. The total for all categories of corrosion technology approximately $ 337 billion annually. The NBS study references an earlier survey of corrosion expenditures segregated by these classifications, Tt indicates that the highest corrosion expenditures are for corrosion resistant alloys which total about 55% of the total, followed in decreasing order by protective coatings (30%), non- metallic (5%), cathodic protection (5%), inhibitors (4%) and testing (1%). Whereas the percentages are good overall indication of expenditures, the amount may vary considerably by industrial sector. Copyright © Hudson Technology & Strategic Studies, Ottawa-Canada 2009Review gonarc Wien Shame of No procedures TE ( Subsea) Eun Updating he maser eae Oren even yer | AERO ADUAOPCO wos tee oie Sine wooo Clipe Oven evry 3003 | Riskesesamen and ie Femeney | (Seen Fisk assessmentrankng of pipelines ‘ADNOG COP VE-01 IEICE Remnantife assesement study No procedures Pipelines Eng alelelslele Coresion management statement of ines Appendix IT Wells Integrity Compliance Check List Produced water analyls Every production test No template ‘ADMA-OPCO approved standardsProcedures/Code No procedure som Gas analysis every 8 month "No procedures (Crude i analyse Every preducton leet "No procesures Scaleldeors analysis [AS and when requred "No procedures. Testing of te annuals ud ‘Once a year No procedures 5 corrosion Eng 8_| Testing of packer tid ‘Once year No pocedres Canosion Eng. 7__| Population of wos production dat ‘Alle te No proceaures ene | Popuaton of Laboratory tng cata ‘ite te No procedures corrosion €9. | Popcation of wale ierventionsaney ‘Alihe tme No possiizes aa 10 | Teing ntemalExeral creson survey When required No procedires ane | Cesing real conaion aurvey very work over No procoaures ‘conosion Eng. 12 | Conductor external coatng assessment | Once ery § Years No procedures Coatngs Eng 13. | Knees ee extemal costing assessment Every 3 years io procesures| Conings Eng 14 | Conductor damp inegiy check Once every 6 Years io procedures Subsea Eng 15 | Conductors OP Potential check Once ovary § Yours DNVRP B4Ot suscea Eng. 16 | Water wat ioc ost entiy No procedures eaees 17 | Butreaaing of shut of wet wats ‘Ones every 2 Years No proceaires canzsion Eng 18 | Completion Mater evaluation Once every § Years No proceares Metfels Coa 19 | Inspection of recovered tubing’ anaete! No procedures Corrosion Eng. 20_| Downhole Scale tendency modeling Once every2 Years io procedures consi Eng 21 | Downhole Coreionpredision meding | _ Once every 2 Years No procedires Coronion Eng 2 | Caen Weare ped ‘Once evary2 Years No proesdures PESEriarsor 73 | Downhole Asphaine peicion modeing | Once every? Years No procedures Corosion Eng, ‘Dump food zane sealing check ‘Once every 5 Years No proceaures Petroleum Eng ‘Reservoir Water movement tacking review ‘Once every 2 Years No procedures corrosion Eng “Teatng/Sereening of eorosion inhibitors ‘Once every 5 Years [No procedures Corosion Eng, Examine the inestion water quality (Once every 3 months No procesures. corrasion Eng Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009identification of wets ze | anita en (Once every year No procetires eieaentat 25_[ Risk ranking of WIS ‘Once every 2 years [ADNOC COF VE-O1 ‘Coresion Eng. 7 ‘Actual 2005, @ [93 [ a4 ‘CORROSION CONTROL Main Pipelines. ‘Chemical Inhibition Production Actual Vs Required no. of checks (%) Supervisor Comptiant checks (%) Dew Point Monitoring ‘Actual Vs Required checks (%) ‘Compliant checks (6) Production ‘Supervisor Production Eng, " Rus Actual Vs Required (nos.) C1 Batch treatment Vs Actual pig Runs (%) Gas Plants. ‘Actual Vs Required no. of Glyeol pli checks % Oil & Gas Prod. Compliant pH checks (%) Supervisor Injection Water Treatment “Actual Vs Required no, of Ch, checks (96) Residual ‘Compliant Cl; checks (%) Sulphite ‘Actual Vs Required no, of O; checks (%) ‘Compliant 02 checks (6) Actual Vs Required no. of Residual Sulphite checks (%) Compliant Residual Sulphite count tests (%) Actual Vs Required no, of SRB count tests (°) ‘Compliant SRB count tests (96) (CORROSION MONITORING Main Pipelines ‘Operational Locations Ws Total nos. (%6) Designated Coupons retrieved Vs Total nos. (%) Cort. Eng. Infield pipelines & Super Complex piping ‘Operational Locations Vs Total nos. (%) Designated ‘Coupons retrieved Vs Total nos. (%) Corr. Eng. ‘CORROSION RATE ACHIEVED Main Pipelines (7 nos.) (46" MGL, 36” MOL, 18” Cond, 4 Nos. Infield line ion Rates Meeting Target (%) Designated Corr. Eng. Corr Infield pipelines & Super Cor ‘Corrosion Rates Meeting Target %) Designated Cor. Eng. 30 Appendix 111 Integrity KPI’s for pipelines Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Instructor Profile Name Abdelaziz M. Salah Eldin Date of Birth 5", March 1959 Nationality Egyptian/Canadian Email aazizS9@yahoo.com Telephone United Arab Emirates (0097150464188 Canada (0016133017051 Cairo (0020100113495 ACADEMIC QUALIFICATION B. Sc Chemistry, Ain Shams University Cairo, Egypt, 1981. M. Sc Chemical Engineering department, Cairo University, 1986 "Secondary and tertiary oil recovery in mature oil reservoir” + MBA Project Management & Strategic Planning, University of North Carolina, USA, 1991 SPECIFIC EXPERTISE AND EXPERIENCES Development, research and implementation of Assets Integrity Management Strategies (PIMS, SIMS, WIMS & CSIMS and implementation tools. Review/endorsement of Certification, accreditation and third parties verification of plant and facilities, Bench marking and application of best practices in corrosion control and introduction of new technology. Asset Maintenance systems diagnostic auditing and integrity assurance reviews, Risk Based Inspection RBI pilot and trials implementation programs. ‘Safety and integrity management systems review, hazard identification and risk assessment, exceptional management reporting for exploration, refining and petrochemical sites. Safety analysis updates, QRA methodology and HAZOP analysis Examination of pipelines integrity compliance, emergency repair strategy and incident preparedness. Design review appraisal, remaining life assessment studies, written schemes. of examination and FFS for subsea pipelines, QA/QC consultancy service agreements from the pre- FEED phase until plant final acceptance and commissioning, Executive Profile 30 years! experiences in Production Chemistry, Corrosion, Coatings, Inspection and Metalic & Non Metallic materials selection. Have the opportunities to work with leading Engineering houses, Major Oil & Gas producers and QA/QC focused ‘organizations provided him with adequate tools to understand the basic needs and deliverables of different engineering disciplines, contractors and service providers throughout the facies life cycle, Abdelaziz has a wide experience _in Upstream & Downstream Oil and Gas projects management and operation interface. He has a good contribution in the development of Assets Corrosion Management Strategies/ Philosophies and relevant integrity assurance issues for many major operators. He Is @ co-founders of Hudson Technology and Strategic studies, Ottawa Canada in 2004. He developed the process, ‘methodology, operation and training scheme for the internationally recognized WEB based Industrial coatings business solution "EP Max" with over 40 copies sold worldwide. Abdelaziz, presented 47 Technical papers as author in many international and regional conferences, During his carrier, he developed over 45 technical specifications and manuals in the field of Corrosion and Integrity management. He has been a project manager and team member for over 80 major quality & integrity management audits and ‘competency analysis projects in association with leading service providers. Currently he Is teaching training courses in Assets Integrity management, Corrosion ‘Management and fundamentals of Coatings ‘and Non Metallic materials Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009Appendix I Pipelines Integrity Compliance Ch Measurements and Data collection | eck List i 1_| Inteligent Pigging Table J-3 of CMS | Pipelines Integrity Management strategy IE ( Sub sea) 2__[ Rouine piging operation Table Sef cus | Gonesion management srategy S10-02 | Producton Sup. 2 [LER NRC STORG ‘Ghee ee"73 | 205 campaign scope ot work acne 4 | Sonomaticsivey Soeime Sever TE (Sub soa) | Pana roquney verfeaon No procedures Coraion Era | Tstnosrenng of coroson rnb Garin Ter Tvieg Eeaion | Sono Eg 7_| Rosiual chemicals check No procedures Conoion Ena 8 | Chemical injection skids relocation ee eee Corrosion Eng, | Gorosioninniitornjectonrateadusiment | Once avery Year_| No procedures Corrosion Eng 10. | Corosen montonng measurements Oncoayeor | Annual srosion Nontorne Campain our 11 | SEERERTERSRE RR Seger Wentorg reece SP eat 12 | Bi protes (SRB) moasroments Every monte | Selon Waring rosa SP wre 12 | festaglereonng of Water Hecion Oregano procedies - "| conocer Ee 14 | ator quality massirmonts at Medes Daly Proton Sup 15 | Water quaitymessirament at Towers | every ¢.days | Water qliy manval Prost Sup 16 | SEE OY INGA wal | — OFS RIET—TNecmare Praises ei 17 | caace protien potntal measurement | e205 | on RP BADH IE (Subsea) 16 | Anodes consumption evel Once ovo | on RP BAOH TE (Sibeo0) 10 | Gly of exe prctectve casing Oneg every | Prveduesforunderateripecton | cosinga Eng 20_| Qualiy of concrete weght costing Ores every | Procedures forundewwatermspecion | Costngs Eng. 21_| Cunt of et jot protsv contng Once every | Prveduestorundewaterpecton | Cootnga ng ca. | Besreker secon sion Ores ee S| Fai sioorene Tar FORSTER | span 23. | Riser clamps integrity Once every 5 | No procedures 1 (Sub sea) 24 | Bots & nuts protection compliance Once every years | No procedures IE (Sibse0) 25_| Flange faces protection compiance nce every years | No procedures IE (Sb sea) 25. | Voloty vericaton Oree ere¥S | Pipsine design manual =| _~Plpetnes Eng 21 | Flow regime verification neg eve 5 | Pipatine design manual Pipolnes Eng 28 | Chomeaisseectonforhyronatotestng | As requed | Noprocedres Cerresion Eng 2e_ | Renfowing toes mabe eSGeress | Once every 2 Vor | Notbatng of pein CP 108 Corin Eng. 30 | neorty ep launcher! receiver ‘Once every3 years | Pipelines itegrty Management oysiem | IE (Sub eo) 31 | Presonaton ofthe pio leuncerRecevers | Omggeey® | Rresenalion flat eavemerts SP: | Conosion Eng 32_| Review of rspecion overdue tars Once evry year_| Work oer flagging & racking systems | IE (Bub sa) 38_| Maintenance epaibectog Once every year | No procedures IE (Sib 209) ax_| beak Roqonoyandrentcase rails | Gace every year | No precedes ——— Copyright ® Hudson Technology & Strategic Studies, Ottawa-Canada 2009