Published on

Published in: Technology, Business
  • Be the first to comment

  • Be the first to like this

No Downloads
Total views
On SlideShare
From Embeds
Number of Embeds
Embeds 0
No embeds

No notes for slide


  1. 1. SPE 155211 Review on Materials for Corrosion Prevention in Oil Industry Anshul Arora, Siddharth Kumar Pandey Rajiv Gandhi Institute Of Petroleum Technology, Rae Bareli, India Copyright 2012, Society of Petroleum Engineers This paper was prepared for presentation at the SPE International Conference and Exhibition on Oilfield Corrosion held in Aberdeen, UK, 28–29 May 2012. This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright. Abstract Among the many challenges faced in production and refining of crude oil, corrosion stands out due to its potential impact and associated economic and safety concerns. The primary cause of corrosion is the presence of mineral acids such as hydrogen chloride formed by hydrolysis of salts present in crude oil. Currently, significant research efforts have been devoted to design and develop new materials and procedures to reduce the water content and neutralize the acids in crude. These efforts have resulted in development of new corrosion-proof materials for coating in pipelines, chemical reagents and surface active substances for neutralization of acids as well as breaking of emulsions. Anionic, cationic and non- ionic surface active reagents are reported to be effective in demulsification application. Particularly the amphiphilic block copolymers, such as polyetyleneoxide-block-polypropylene oxide are used globally for the process of demulsification. Various organic amines are used in the overheads of atmospheric columns for neutralization of acids. Numerous nitrogenated compounds are also used as corrosion inhibitors in different refining operations. HERCULES-30617, KEMLIX-1123X and DEOL-4241 are some of commercial names used for the purpose of corrosion inhibition. Hence we are deeply motivated to review all the recent research progresses that will provide us the impetuous to analyze the existing shortcomings and design and develop new materials with possible applications in above mentioned areas. Keywords: Corrosion, demulsification, inhibition, anionic, electrochemical 1. Introduction: Oil industry that is production, transportation and processing of oil consumes 8% of all metal which is made in the world. At the same time, oil industry is characterized by high corrosive activity of media at all the stages of production, transportation and processing of oil. In this industry the corrosive wear of metal determines duration and fail-safety of equipment, duration of overhaul periods and expenses of equipment repairs. Losses caused by corrosion consist not only of the loss of metal mass but also cause worsening of equipment functional properties. Latter considerably exceed direct losses, such as suspension of production, explosion, fires, ecological catastrophes related to the accidents on oil and gas pipelines, damage of reservoirs, piping, breakage of vehicles, surface and underground structures, etc. The presence of corrosive components in transported fluids negatively affects metal in oil production,
  2. 2. 2 SPE 155211 refinery, transportation and processing operations. The degree of corrosive damage to oil production equipment is determined by the degree of heterogeneity of the extracted fluid, the content of corrosive gases (carbon dioxide [CO2] and/or hydrogen sulphide [H2S]), the degree of mineralisation in the aqueous phase and the variability of the corrosion activity of technological media in the course of exploration of a given deposit. In today’s industrial world there is a focus on cost savings and there is a continuous search for new innovative technologies and solutions to extend the working life of existing assets and infrastructure while lowering environmental impact. The world of pipelines is no different in its search for smarter and greener solutions. As a large number of liquid transport pipelines continue to mature and maintenance and operating costs continue to rise there has been an increased focus on finding environmentally friendly, innovative solutions to achieve these goals. In spite of much advancement in the field of corrosion science and technology, the phenomenon of corrosion (mainly of Fe, Al, Cu, Zn, Mg and their alloys) remains a major concern to petroleum industry. Though the serious consequences of corrosion can be controlled to a great extent by selection of highly corrosion resistant materials, the cost factor associated with the same, favours the use of cheap metallic materials along with efficient corrosion prevention methods in many industrial applications. In this aspect, corrosion inhibitors have ample significance as individual inhibitors or as a component in chemical formulations [1]. A large number of corrosion inhibitors have been developed and used for application to various systems depending on the medium treated, the type of surface that is susceptible to corrosion, the type of corrosion encountered, and the conditions to which the medium is exposed [2]. 2. Discussion: In most environments, metals are not inherently stable but tend to revert to compounds, which are more stable; a process with is called corrosion [3]. Corrosion is derived from the Latin "corrosus" meaning gnawed away. The definition of corrosion is "the chemical or electrochemical reaction between a material and its environment that produces deterioration of the material or of its properties". On the other hand, corrosion is considered as including combined forms of attack in which the simultaneous occurrence of corrosion by chemical or electrochemical attack [4,5]. The chemical attack or dry corrosion occurs under dry conditions, such as high temperatures in gaseous environments, molten salts and liquid metals. Dry corrosion process is a direct reaction between a metal and the corrosive environment. Dry corrosion is of great importance in a number of petroleum refining processes. It includes the attack of hydrogen sulphide and other sulfur compounds on steel and various alloys at elevated temperatures. Solutions to this type of corrosion generally depend on metallurgical approaches, e.g. variations in composition, heat treatment of the selected metal or alloy. Wet corrosion is an electrochemical process; in practice it is limited to nearly 232 ºC as an upper temperature. The electrochemical corrosion results from reaction between a metal surface and an ion-conducting environment. This process can occur if the metal contact with an electrolyte for transport of electric current. Most cases of electrochemical corrosion proceed in aqueous media such as natural water, atmospheric moisture, rain, and wet soil. Also, other environments e.g. acids, petroleum products, cooling water, chemical solutions etc. For example, water is presented in refinery by different sources, such as the crude itself, through injection of water of steam to aid in the steam distillation of various petroleum fractions, water washing or aqueous solution contacting various intermediate and product streams in refining and petrochemical processes. In refineries, acid (lower pH) attacks the active metals such as Fe, Cu, Zn, Al and others[6] As a rule, surface –active substances which produce a protective film over metal surface are inhibitors. Inhibition is one of the simplest and economical methods of corrosion protection, However inhibitors must meet following requirements: maximum protective action and minimum consumption; absence of influence on the technological process proceeding, quality of products and work of catalyst. they should be soluble or dispersible in water or brine, they should pass to an organic phase in insignificant amounts
  3. 3. SPE 155211 3 only, they should not create emulsions in water and condensates, they should be easily separable, they should ensure a highly protective effect, they should prevent the formation of pitting, they should prevent the hydrogenation of steel (in the case of the presence of H2S), they should be non-toxic and they should have strong after-effects. Along with strong protective properties, another important requirement for inhibitors is that their foaming and emulsifying abilities should be low, since foaming and emulsification may impair the operating process of oil treatment: a corrosion inhibitor might cause a working solution to foam, which would disturb the operation of the system. Systems for complex oil treatment for transportation separate hydrocarbons–water liquid mixtures to isolate an oil fraction. The corrosion inhibitors used to protect equipment and pipelines should not decelerate the separation of the oil–water mixture. They must be economic, stable and harmless for attending personnel and the environment. The inhibitors are classified according to their effect on the electrochemical reactions, which make up the overall corrosion process, into three main types [7,8]: 2.1 Anodic Inhibitors: These inhibitors affect the anodic reaction and its polarization curve. They show an increase in the polarization (a large potential change results from a small current flow). The anodic reaction whereby a metal dissolves while releasing electrons is: Fe Fe2+ + 2e (1) or is converted into solid compound, such as: 2Al + 3H2O Al2O3 + 6H+ + 6e (2) The potential shifts to more positive direction (anodic direction), as shown in Fig. 1 [9]. The anodic inhibitors function to reduce the dissolution rate of the passivating oxide [10] to repassivate the surface by repairing or reformation the oxide film, to repair the oxide film by plugging pore with insoluble compounds and to prevent the adsorption of aggressive anions. An example of this type of inhibitors is chromate ions, which must be replaced by more environmentally inhibitors, such as rare earth elements [11, 12], also, molybdate, nitrite and phosphate [13]. Organic compounds such as formaldehyde, pyridine and polyethylene polymer used to inhibit steel corrosion. These types of inhibitors are considered "dangerous inhibitors", especially, at lower concentrations pores and defects can arise on the oxide layer, where the attack will be increased causing corrosion acceleration. Fig 1. Schematic diagram shows effect of inhibitors on polarization curve.
  4. 4. 4 SPE 155211 2.3 Cathodic Inhibitors: These types of inhibitors are mainly influence the cathodic reaction and the cathodic polarization curve, as shown in Fig. 1. For example, cathodic reaction proceeds in acid solution: 2H+ + 2e H2 (3) Potential shifts towards more negative values (cathodic direction). Examples of the cathodic inhibitors are polypposphate (sodium polyphosphate (Na2P2O7), Sodium tripolyphosphate (Na5 P3O10). Organic compounds such as N-heterocyclic e.g. imidazole and benzimidazole. These inhibitors are added to boilers to prevent adherent deposites of calcium and magnesium [14]. There are some cathodic inhibitors such as arsenates, sulfides and selenides used to poisons the cathodic process by interferring with the cathodic reaction (hydrogen atom formation and hydrogen gas evolution in acid medium, equation 3). These inhibitors are environmentally unacceptable because they are toxic [15]. Generally, cathodic inhibitors are considered "safe inhibitors", because they provide inhibition of the cathodic reaction even with a very low concentartion of the inhibitor. 2.4 Mixed Inhibitors: These inhibitors work to inhibit both anode and cathode reactions, as in Fig. (1). Benzotriazole is used widely for copper and copper alloy protection [16, 17]. Quniolines and thiourea used to inhibit the dissolution of mild steel in H2SO4. Amines, amides, acridines used to inhibit steel corrosion in HCl. The inhibition is accomplished by one or more of some mechanisms such as [18, 19]: 1. Some inhibitors retard corrosion by adsorption to form a thin and invisible film on the material surface. 2. Others form visible bulky precipitates, which coat the metal and protect it from attack. 3. Another common mechanism consists of causing the metal to corrode in such a way that a combination of adsorption and corrosion product forms a passive layer. The inhibitor can be transported to the metal surface from [20]: - A liquid corrosive environment, in which the inhibitor is present in dissolved or dispersed form. - A corrosion preventing fluid with an additive of inhibitor. - The atmosphere in a package, in this case inhibitor is required having a suitable vapour pressure. It is called volatile corrosion inhibitor or vapor phase inhibitors. They are transported in a closed system to the site of corrosion by volatilization from a source. In boilers, volatile inhibitors such as morpholine or octadecylamine are transported with steam to prevent corrosion in condenser tubes by neutralizing acidic carbon dioxide. In closed vapor spaces, such as shipping containers, volatile solids such as carbonate, and benzoate salts of dicyclohexylamine are used. Different organic compounds containing nitrogen, sulphur, oxygen, phosphorus, silicon or other substances are used as inhibitors. Petroleum refining mainly uses nitrogenated-containing compounds as inhibitors. Inhibitors soluble in a hydrocarbon phase have undoubted advantages. They are able to form hydrophobic film over surface of metal. The first step of inhibitor action is water displacement. The ability to displace water and aggressive liquids from the surface of metal mainly determines protective efficiency of inhibitor. The chemisorptions layer of inhibitor formed over the metal surface is the main component of protective action. Chemisorption is determined by forces of chemical interaction which predetermines considerable energy of connection between inhibitor molecules and metal surface. At adsorption on the surface of iron or other metal containing uncompleted d-sublevels, organic inhibitors serve as donors and metallic ion-as acceptors of electrons. Strength of adsorption connection depends on
  5. 5. SPE 155211 5 electronic density over the adsorption-active area of inhibitor molecule. That is why the protective effect of inhibitors must be related to the parameters which characterize electronic-donor properties of molecules. Atoms with unshared electronic pair or areas containing p-bound electrons are main adsorption areas in the inhibitors molecule.There are three types of inhibitors: Chemisorption compounds of donor type (sulphonates , amides); chemisorptions compounds of acceptor type( amines, amides, organic acids, surface-active compounds aontaining phosphorus or sulphur in their molecule); fast-acting SAS of screening typr(oxides petroleum products, such as paraffins, petroleum , as well as fatty acids, glycerides, fats). As inhibitors are used compounds containing the following molecular fragments: Molecules which have a free electronic pair, as well as p-electron are presented in these fragments. Thus, these inhibitors belong to the latter two types listed above and can operate using all possible mechanism of corrosion inhibition. Development of such inhibitors will allow, obviously, obtaining products with wide spectrum of application. Presently, most of inhibitors which are used in petroleum refining are derivatives of imidazoline [21]. There are the same problems of choice of the optimum composition when using imidazoline, as well as using other inhibitors. The system may be treated in any place. It means that inhibitor may dissolve or easily disperse in water or in oil. Plenty of corrosion inhibitors are presently for metal defence. The large assortment of these matters is explained by variety of media and conditions under which inhibitors are used. Moreover, many chemical compounds have inhibiting properties. Inhibitors of TAL-M type were widely used in industry for the corrosion protection of apparatus and equipment [22]. Corrosion takes place under the action of oil, gas condensates, brines and products of water condensates (which contain the dissolved aggressive gasses, such as chlorous hydrogen, carbon dioxide, hydrogen sulphide, etc). The package of ―Hercules‖ reagents is developed by the laboratory of technology of oils preparation of JSC‖VNIP‖ (Russia). ―Hercules-30617‖ was tested for a corrosion protection of condensation refrigeration equipment (CRE) of the primary oil processing plants [23]. The result obtained testifies that ―Hercules‖ reagents provide the effective corrosion protection of equipment. Industrial application of Kamelix 1123X corrosion inhibitor, produced by ISI firm (Great Britain) showed satisfactory results. It is recommende to add 3-5 g/ton of this film –forming inhibitor.‖RENA- Naftokhim -8‖ inhibitor is intended for the corrosion protection of oil-and-gas equipment and water-pipes which support layer pressure. Corrosion is caused by hydrogen sulphide, carbonic acid, and mineralized stratal waters. ―DEOL-4241‖ inhibitor is intented for corrosion protection of apparatus and equipment in the media of oil, aqueous solution of salts, condensates, hydrocarbons and water vapours, aggressive gasses [24]. It is an inhibitor with optimal composition consisting of amides and polyamine naphthenic acids. Hydrophobic layer is formed due to the amide adsorption over the metal surface. Such a layer prevents interaction between aggressive medium and metal. Interaction between amine and sulphuretted hydrogen (or HCl) neutralizes the main part of acid gasses. The inhibition in oil and gas field is more complicated and requires specialty inhibitors depending on the area of application such as in refineries, wells, recovery units, pipelines etc. Aggressive gases such as H2S, CO2, and organic acids complicate the problem of inhibition in wells. Corrosion problems in petroleum refining operations associated with naphthenic acid constituents and sulphur compounds in crude oils have been recognized for many years. It is particularly severe in atmospheric and vacuum
  6. 6. 6 SPE 155211 distillation units at higher temperatures, 175-400 °C. Dissolved O2 is the main species causing corrosion in recovery units. Dry corrosion is of great importance in refinery processes. HCl may form in refineries as a by-product. O2, CO2 and H2S intensify corrosion problems in natural gas pipelines. Wet corrosion in refineries can be controlled by passivating, neutralizing or adsorption type inhibitors. Slag inhibitors are used along with the corrosion inhibitors to reduce deposits. Both water soluble and oil soluble inhibitors are used in pipelines. Adsorption type inhibitors are widely used for preventing internal corrosion of pipelines carrying refined petroleum products. In general, where the operating temperatures and/or the acid concentrations are higher, a proportionately higher amount of the corrosion inhibitor composition will be required. It is preferable to add the inhibitor composition at a relatively high initial dosage rate, about 2000 to 5000 ppm, and to maintain this level for a relatively short period of time until the presence of the inhibitor induces build-up of a corrosion protective coating on the metal surfaces. Once the protective coating is established, the dosage may be reduced to an operational range, about 10 to 100 ppm. It is known that nitrogen based corrosion inhibitors are relatively ineffective in the high temperature environment. Also, the phosphorus-containing compounds may impair the function of various catalysts used to treat crude oil. Catalytic polymerization of tall oil fatty acids such as oleic and linoleic acids give varying amounts of dimerized and trimerized fatty acids. These dimer and/or trimer fatty acids may be neutralized with an appropriate amine; which the oil industry has traditionally employed as an oil-soluble inhibitor for reducing corrosion in oil well piping and related recovery equipment. Over the years, the corrosion inhibition art has looked for alternatives to the dimer/trimer acid-based product. Of particular interest in this regard is the class of fatty acid-based products which have been functionalized with maleic anhydride and/or fumaric acid. The fatty acids can first be maleated followed by an oxidation. Alternatively, the fatty acid material can first be oxidized and then the oxidized fatty acid product can be maleated [25]. Zagidullin et al. patented a terephthalic acid based method for corrosion inhibition. An acid inhibitor is prepared by interaction of polyethylene-polyamine with terephthalic acid at 150-190 0 C for 4-8 h in the molar ratio of 2:1, followed by reaction with benzyl chloride at 80 0 C for 5 h. The product was used as a component along with urotropin and neonol in water [26]. Rhodanine (2-thioxo-4- thiazolidinone) and its 3- or 5- derivatives are patented as a Fe corrosion inhibitor of oil refining equipment in carbonic acid derivatives [27]. Zetlmeisl et al. disclosed a method for inhibiting naphthenic acid corrosion at high temperatures based on novel thiophosphorus compounds [28]. Subramaniyan et al. patented a polyisobutylene phosphorous sulfur compound as corrosion inhibitors for high temperature naphthenic acid corrosion and sulphur corrosion. This results in improved performance as well as a decreased phosphorus requirement. The compound is obtained by reaction of high reactive polyisobutylene with P2S5 in presence of sulphur powder [29]. Huang et al. patented a reaction product of thiophosphate (produced by reaction of phosphide with fatty alcohols) with spiro-diester (product of reaction of alkenyl succinic anhydride with organic amine using inorganic salts as catalyst) as high temperature corrosion inhibitor [30]. Alykov et al. patented 1-nitro-3,3- diphenyl-1-[3-(3- nitrophenyl)-1,2,4-oxydiazol-5-yl]-2,3-diazoprop-1-ene, that was obtained by condensation reaction of equimolar quantities of substituted 3-aryl-5-nitromethyl-1,2,4- oxadiazol with 1,1-diphenylhydrazine in ethoxyethane medium; as corrosion inhibitor for metal protection against acid corrosion in oil and gas pipelines for non-alloyed steels [31]. Strak et al. patented a method for inhibiting corrosion in a separation unit that comprising treating the unit with inhibitors selected from the group consisting of dodecenyl succinic acid, and di-hexyl succinic acid [32]. Leinweber patented low toxic, water soluble and biodegradable corrosion inhibitors of metal salt of CH3SCH2 CH2 CH (NHCOR) COOH containing anionic and cationic surfactants [33, 34]. Bhat et al. disclosed a non chromate aqueous corrosion inhibitor composition for metallic surfaces exposed to medium of pH 4, comprising of an anodic corrosion inhibitor (ammonium heptamolybdate/sodium orthovanadate), a cathodic corrosion inhibitor (cerium chloride) and a metal complexing ligand (trisodium citrate-2- hydrate); dissolving the blended product in water as 2.5 wt.% solution [35]. Nacetyl- 2-(2,3- dihydroxycilopentenyl) aniline with concentrations 50-200 mg/L was proposed as an inhibitor of corrosion in mineralized water petroleum solutions including H2S [36]. 2-propyl-3-ethyl-8-
  7. 7. SPE 155211 7 oxychinoline-ZnCl2 complex was disclosed as a steel corrosion inhibitor for petroleum production applications in mineralized media with high O2 content. The compound is manufactured by condensation of ZnCl2 containing o-aminophenol with an oil aldehyde in benzene followed by reaction with ZnCl2 [37]. Acidic fluids (HCl, HF etc) are often used as a treating fluid in wells penetrating subterranean formations for cleanup operations or stimulation operations for oil and gas wells. Corrosion inhibitor intensifiers have been used to extend the performance range of a selected acid corrosion inhibitor. Most intensifiers such as KI, Sb-based compounds etc have temperature, time, and environmental drawbacks. Wilson e al. disclosed 2-chloro-2,2-diphenylacetic acid and 2- bromoisobutyric acid as corrosion inhibitor intensifiers [38]. Beloglazov et al. disclosed an antipyrine derivative as aninhibitor against microbilogical (myxromycete) corrosion of equipment made of carbon steel and alloy steel with cadmium coating [39]. One of the causes of wear in an internal combustion engine is corrosion of the metal surfaces of the engine. The corrosion promoting compounds present in the crankcase are principally weak organic acids which may result from nitration and oxidation of the lubricating oil due to contamination by blow-by gases and exposure of the lubricant to high temperatures. For the purpose of preventing corrosivity by these compounds on the various engine parts, it is necessary to incorporate dispersants, detergents, and corrosion inhibitors in the lubricating oil composition. It is desirable to minimize the amount of phosphorus in lubricants. Although phosphorus does not contribute to ash, it can lead to poisoning of catalysts. Boudreau disclosed a lubricant composition containing P and S free organotungstates imparting improved antiwear, corrosion, and antioxidant properties. The organic tungsten complex is a reaction product of a mono- or diglyceride and a tungsten source, or of a secondary amine, a fatty acid derivative and a tungsten source [40]. Corrosion inhibitors such as oil soluble 2,5-dimercapto-l,3,4- thiadiazole or hydrocarbyl- substituted 2,5-dimercapto-l,3,4-thiadiazole derivative was used in a patented lubricating composition by Tipton etal. [41]. Na or Ca salt of dinonylnaphthalene-sulfonic acid was used as a corrosion inhibitor in vegetable oil based lubricants [42]. A patented phosphorous free additive composition contains a hydrocarbyl-substituted 1, 2, 4- triaxole corrosion inhibitor [43]. Ivanov et al. disclosed an inhibitor composition as additives into motor oils and lubricating cooling liquids that contains a lanthanum oxide, triglycerides of higher carboxylic acids, alkylbenzenesulfonic acid, alkanolamine, lanthanum nitrate and organic solvent in the balance [44]. 2.5 Application of corrosion inhibitors: Most of the described above corrosion inhibitors are widely used and continue to be used in oil industry of Ukraine. However, determination of efficiency of these inhibitors was carried out under different conditions (temperatures, inhibitors, consumption, aggressiveness of media, etc.). So, we decided to compare efficiency of inhibitor used in Ukraine under identical conditions. Efficiency of Dodicor 3747, Kamelix 1123 X, 25-13-R, RENA-Naftokhlim-8 and DEOL-4241 inhibitors were compared. Inhibitor consumption was in the range of 10-100 g/ton depending upon medium corrosiveness. Experiments were carried out by researchers in monophase and diphasic media. The results of the research of inhibitor efficiency in a monophase medium are presented in Fig 2[44].
  8. 8. 8 SPE 155211 Fig 2. Inhibitor protective effect in monophase medium. Inhibitor specific consumption was in the range of 50-100 g/ton. The low level of protective action of all inhibitors is explained by high corrosive activity of the medium. Under the desired condition Kamelix 1123X, TAL-25-13-R, RENA-Naftokhlim-8 and DEOL-4241 had the greatest efficiency. Other inhibitors showed less protective action in the investigated monophase medium. The results of the researches of inhibitor efficiency in diphasic medium are presented in Fig 3[44]. Fig 3. Inhibitor protective effect in diaphasic medium. P R O T E C T I V E E F F E C T % Dodicor 3747 Kamelix 1123 X AKS OR-2K TAL-25-13-R DEOL-4241 RENA-Naftokhlim-8 P R O T E C T I V E E F F E C T % Kamelix 1123 X DEOL-4241 TAL-25-13-R AKS OR-2K RENA-Naftokhlim-8
  9. 9. SPE 155211 9 Similar to previous cases Kamelix 1123X, TAL-25-13-R, RENA- Naftokhim-8 and DEOL-4241 had the greatest efficiency. DEOL-4241 was the most effective at consumption equal to 10g/ton. At consumption of 25g/ton its efficiency is commensurate with efficiencies of TAL-25-13-R and RENE- Naftokhim-8 inhibitors. The increase of specific consumption of AKS and OR-2K inhibitors higher than 25g/ton practically does not influence their efficiencies. One can see that inhibitor efficiency depends on its concentration in an aggressive medium and on medium nature. Graphic comparison of inhibitor efficiency in different media at the specific consumption of 50g/ton is represented in Fig 4[44]. Characters of inhibitors action are different. Some of them have low efficiency both in monophase and in diphasic media, e.g. OR-2K and AKS. Some of them have high efficiency in both media, e.g. DEOL- 4241, TAL-25-13-R, Kamelix1123-X, RENA- Naftokhim-8. Fig 4. Inhibitor protective effect in monophasic and diaphasic media at specific consumption of 50g/ton 3. Conclusion: Different kinds of inhibitor can be used to protect equipments and pipelines from corrosion by the many corrosive media used in oil industry. However, in many cases the implementation of accumulated experience and its formal transfer from one deposit to another is ineffective. It is necessary to select the optimum protective measures, including inhibitors, in each particular case. R&D in different areas of corrosion inhibitors is exploring newer methods and products. Recent works in the field of corrosion inhibition are reviewed here and are presented according to the area of application of the inhibitors. Conventional inorganic inhibitors continue to be a major component in many patented inhibitor combinations. Few novel inhibitors are introduced. Many of the reports deal with novel inhibition methods in various applications. We can conclude that efficiencies of explored inhibitors depend on their specific consumption and medium nature. Experimental results carried out by researchers shows that DEOL-4241, RENA – Naftokhim-8, TAL-25-13-R and Kamelix 1123X are most effective inhibitors. Efficiencies of these demulsifiers are commensurate. They have the same high efficiency both in monophase and diphasic media. Expedience of the application of any corrosion inhibitor can be determined only after investigation and production tests and correlation of inhibitor consumption with its cost. P R O T E C T I V E E F F E C T % Kamelix 1123 X DEOL-4241 TAL-25-13-R AKS OR-2K RENA-Naftokhlim-8
  10. 10. 10 SPE 155211 References: [1] Nathan CC. Corrosion inhibitors. National Association of Corrosion Engineers: Houston 1973 [2] Sastri VS. Corrosion inhibitors, principles and applications. New York: John Wiley and Sons 1998. [3] Heusler KE. Present state and future problems of corrosion science and engineering.Corrosion Sci 1990; 31: 753. [4] During EDD. Corrosion Atlas. 3rd ed. NewYork: Elsevier Science 1997. [5] Craig HL. Naphthenic acid corrosion in the refinery. Corrosion95. National association of corrosion engineers, Houston: Texas 1995; p. 333. [6] Corrosion Preventive Strategies as a Crucial Need for Decreasing Environmental Pollution and Saving Economics, A.A. El-Meligi, Recent Patents on Corrosion Science, 2010, 2, 22-33 [7] Thomas JGN, Shreir LL. Corrosion. London: Newers-Butter Worth 1976; vol. 2: p. 18. [8] Trabanalli G. Corrosion mechanism. Chap. 3. Corrosion inhibitors. In: Mansfeld F, Ed. New York: Marcel Dekker 1987. [9] Nathan CC. Corrosion Inhibitors. NACE, Houston: Texas 1981. [10] Uhlig UH. Corrosion and corrosion control. Chap 16. New York: John Wiley and Sons 1963. [11] O’Keefe JM, Geng S, Joshi S. Cerium-based conversion coatings as alternatives to hex chrome: Rare-earth compounds provide resistance against corrosion for aluminum alloys in military applications. Met Finish 2007; 105: 25. [12] Gunasekaran G, Palanisamy N, Appa Rao BV, Muralidharan VS. Synergistic inhibition in low chloride media. Electrochim Acta 1997; 42: 1427. [13] Blin F, Leary SG, Wilson K, Deacon GB, Junk C, Forsyth M. Corrosion mitigation of mild steel by new rare earth cinnamate compounds. J Appl Electrochem 2004; 34: 591. [14] Munn P. The testing of corrosion inhibitors for central heating systems. Corros Sci 1993; 35(5-8): 1495. [15] Munn P. The testing of corrosion inhibitors for central heating systems. Corros Sci 1993; 35(5-8): 1495. [16] Lorenz WJ, Mansfeld F. Determination of corrosion rates by electrochemical DC and AC methods. Corrosion Sci 1981; 21:647. [17] Aksut AA, Lorenz WJ, Mansfield F. The determination of corrosion rates by electrochemical D.C and A.C methods — II.Systems with discontinuous steady state polarization behavior. Corrosion Sci 1982; 22: 611. [18] Trethewey KR, Chamberlain J. Corrosion for science and engineering. 2nd ed. New York: Longman Group Limited 1995. [19] During EDD. Corrosion Atlas. 3rd ed. NewYork: Elsevier Science1997. [20] Mattsso E. Basic Corrosion Technology for Scientists and Engineers. 2nd ed. The Institute of Material Science: London 1996. [21] Topilnitskij P. Lepak V. And Litvyn B. : Materialy konferencii‖ Razrabotka, proizvodstvo i primenenie khimicheskih reagentov dlya neftyanoi i gazovoi promyshlennosti‖, 2002, Moskwa [22] Faizullin Sh., Mashkov V., Semenov E., Koshchii V., Nesterenko S. And Bogatchuk Yu,: Neftepererabotka i neftekhimiya, 2003,10,50. [23] Kostenko A. Et al. : Neftepererabotka i neftekhimiya, 2004, 6,36. [24] TU U 23.2-22340203-036:2006 Inhibitor corrosii‖DEOL-4241‖. [25] Hurd PW, Fultz GD, Neumann BA. Maleated and oxidised fatty acids as corrosion inhibitors for petroleum related applications. US patent 179570, 2008. [26] Zagidullin RN, Rysaev US, Abdrashitov MY, Rysaev DU, Kozyreva YP, Mazitova IS, Bulyukin PE. Method of preparing corrosion inhibitor by reaction of polyethylene- polyamine with terephathalic acid. RU patent 2357007, 2009. [27] Reznik VS, Khodyrev YP, Akamsin VD, Galiakberov RM Giniyatullin RK, Semneov VE,Galyametdinova IV. Method of iron corrosion inhibition of oil-refining equipment in carbonic acid derivatives. RU patent 2351690, 2009. [28] Zetlmeisl MJ, Harrell BG, Borgard BG, Scott B. Method and compositions for inhibition of naphthaneic acid induced corrosion, US patent 001125, 2008. [29] Subramaniyam M. High temperature naphthenic acid corrosion Inhibition using organophosphorous sulphur compounds and combinations thereof. WO patent 120236,2008. [30] Huang Z, Gu X, Teng H, Chen J. Preparation method of high temperature corrosion inhibitor for petroleum refining apparatus and its application. CN patent 101367836, 2009. [31] Alykov NM, Tyrkov AG, Pichugina EA, Tyrkova EA. Inhibitors of acidic corrosion for protection of oil and gas pipelines. RU patent 2365679, 2009. [32] Stark JL, Metzler RD, Babic K. Method for inhibiting corrosion of metal in distillation units caused by organic acids. WO patent 032817, 2009. [33] Leinweber D, Feustel M. Corrosion inhibitors containing anionic surfactants. EP patent 2031094, 2009. [34] Leinweber D, Feustel M. Corrosion inhibitors containing cationic surfactants. EP patent 2031095, 2009. [35] Bhat S, Prasad SR, Talukdar MK, Katarki MV, Sonawane AK, Deshpande AR. Noncarcinogenic corrosion inhibition for oil and gas well completion & packer fluids. WO patent 084503, 2008. [36] Abdrakhmanov IB, Mustafin RN, Chernova AG, Chernova VA, Gataullin RR. Protection method of steel against corrosion in mineralized water petroleum medium. RU patent 2353708, 2009. [37] Khusnutdinov RA, Laptev AB, Bugai DE, Shchepetov AE. 2- Propyl-3ethyl-8oxychinoline- ZnCl2 complex as inhibitor of steel corrosion in mineralized media with high oxygen content for petroleum production applications. RU patent 2365584, 2009. [37] Wilson JM, Cassidy JM, Kiser CE. Corrosion inhibitor intensifier compositions and associated methods. US patent 139414, 2008. [38] Beloglazov SM, Myamina MA, Gribankova AA. Application of antipyrine derivative as an inhibitor against myxromycete corrosion and steel hydriding in a water salt medium. RU patent 2359068, 2009. [39] Boudreau D. Organic tungsten complexes. WO patent 116099, 2008. [40] Tipton CD, Sumiejski JL, Abraham WD. Multi-dispersant lubricating composition. WO patent 014319, 2008. [41] Thoen JA, Geiger R, Greaves MR, Busby DC. Miscible lubricating oil blends of glyceridic vegetable oils and polyethers or polyoxyalkylenes. WO patent 134179, 2008.
  11. 11. SPE 155211 11 [42] Hutchison DA, Dittmeier RT. Triazole alkyl derivatives as corrosion inhibitors for machines, power generating equipment and engines. US patent 139425, 2008. [43] Ivanov DM, Ivanov MG. Inhibitor of metal corrosion used as additives into motor oils, lubricating-cooling liquids. RU patent 2347011, 2009. [44] Corrosion Protection of Oil Production and Refinery Equipment, Chemistry and Chemical Technology, Vol. 1, No.1, 2007