Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 Energy Sources, Part A, 35:22-31, 2013 Taylor & Francis Copyright © Taylor & Francis Group, LLC sterans cre ISSN: 1556-7036 prinv/1556-7230 online DOI: 10.1080/15567036.2011.619630 The Clean Up of Asphaltene Deposits in Oil Wells M. Zoveidavianpoor,! A. Samsuri,! and S. R. Shadizadeh* ‘Faculty of Petroleum & Renewable Energy Engineering, Universiti Teknologi Malaysia, Johor, Malaysia *Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran Asphaltene is deposited in all of the petroleum production systems. Normally, wellbore soaking by xylene with bullheading or coiled tubing is conducted to remove these plugs from a production system. However, these operations are frequent and asphaltene continues to deposit shortly thereafter. This article reviews the deposition of asphaltene in petroleum production systems and discusses technical challenges and health, safety, and environmental issues related to the cleanup of asphaltene in oil wells. Keywords: asphaltene, health, safety and environment, solvents, stimulation, xylene 1, INTRODUCTION The main purpose of stimulation is to enhance the property value by the faster delivery of the petroleum fluid and/or to increase ultimate economic recovery (Economides and Nolte, 2000). During the stimulation job, xylene is injected into a well to perform certain functions, such as dissolution, and removal of organic deposits, such as asphaltene, in surface facilities, wellbore, and producing formation. Asphaltene is the term given the to black, carbonaceous components of petroleum, which occur in many crude oils in the form of colloidal, suspended, solid particles. Under static reservoir conditions, asphaltenes are normally held in a stable suspension by resins, a family of polar molecules. As shown in Figure 1, asphaltene deposition generally appears in the field first in the surface facilities, such as flowlines, and separators as the pressure of the asphaltenic hydrocarbon decreased. Its deposition within tubing is directly formed at a depth corresponding to the bubble pressure of produced oil. Subsequently, the asphaltene deposit zone could be formed to the bottomhole and near wellbore formation as reservoir depletion proceeds. Changes in fluid temperature and pressure that are associated with oil production from the reservoir may cause the asphaltenes to flocculate and precipitate out of suspension and adsorb to the rock or pipe surfaces creating production problems for producers by reducing production rates and increasing the possibility of expensive mechanical failure. Furthermore, severe pressure drop, wettability reversal, permeability reduction, plugging of production system, and, finally, lessening of production rate are associated with asphaltene precipitation. Figure 1a shows the schematic of a production system that consists of a reservoir, completion, tubing, wellhead, flowline, and “Address correspondence to Dr. Mansoor Zoveidavianpoor, Faculty of Petroleum & Renewable Energy Engineering, Universiti Teknologi Malaysia, Johor Bahru, Johor 81310, Malaysia. E-mail: mansoor353@ Yahoo.com 22Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 CLEAN UP OF ASPHALTENE DEPOSITS IN OIL WELLS 23 4m Wettend samen [ Fowtine a yo ee Completion @ ‘Occurance of asphaltene depostion in ae time ofan asphaltic well Reser ‘conn wee Fevtne ‘ere Producto Stem Components ) FIGURE 1 (a) A schematic of a production system, (b) occurrence of asphaltene deposition in a lifetime of an asphaltenic well, (€) degree of severity of asphaltene deposition in a production system, (4) pressure trend, (@) temperature profile, and (f) GOR profile. (continued) separator. As an example of an asphaltenic well in the south of Iran, the deposition of asphaltene in its 20 years’ lifetime is shown in Figure 1b, As it is clear in this figure, the plugging first appeared in the surface facilities during the oil final depressurization step in its early lifetime, and advanced with the depletion to the near wellbore region. The degree of severity of asphaltene plugging in the production system is illustrated in Figure 1c. The severity, which consists of various factors, such as economic, downtimes, environment, and so on, is incteased from 1 to 10. Pressure, temperature, and gas-oil-ratio (GOR) profiles in the production system are shown in Figures 1d, le, and 1é, respectively.Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 24 © M. ZOVEIDAVIANPOOR ET AL, Dagee Sey spate pnten apace Degree of every Fase conouon Tee Poe Sewer Prtucon Sytem Cmpenents © 00 Panes edn apictennsten 200 im E 2x0 100 evr ‘conoon Tre Foutne Sear Praucion Sten comport @ FIGURE 1 (Continued) ‘Under normal production conditions, this asphaltene deposition cannot be eliminated, but can only be minimized. A pressure and temperature reduction may cause an arca of an instability, or asphaltene deposition envelope as described by Taritis and Mansoori (1988). The effect of a change in well pressures on asphaltene behavior may be to shift the tendency to precipitate the asphaltene (Monger and Fu, 1987). A change in petroleum fluid properties, such as GOR (Kokal et al., 2005), is believed to have a considerable contribution on asphaltene precipitation.Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 CLEAN UP OF ASPHALTENE DEPOSITS IN OIL WELLS 25 amperes (Ong F) Protuctn tam Components ©) (OR pote mapa ye FIGURE 1 (Continued), This article presents the HSE and technical challenges of xylene and tries to create awareness with the upstream petroleum industry from the xylene usage consequences. As a result, specific regulations and recommendations regarding xylene usage are worth being introduced. Both aspects, environmental and technical, of xylene will briefly be discussed. There is no relevant case study about HSE impacts of xylene in the upstream petroleum industry in Iran, Further, available cases of HSE impacts of xylene that performed in a downstream oil industry are presented in the nextDownloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 26 © M. ZOVEIDAVIANPOOR ET AL, section, Afterwards, utilization of this solvent in reservoir stimulation will be discussed along with a case study in K reservoir, Iran 2. HSE CHALLENGES OF XYLENE Because of the flow back of xylene after well stimulation job, and also the related activities, such as transportation, conservation, and blending prior to utilization, protecting the staffs health should be considered as a critical task for operation companies. Thus, they must have sufficient knowledge of xylene HSE impacts. To be familiar with this important subject, a brief review on xylene health effects and its related rules, regulations, and recommendations is presented in this section. ‘The health effects of xylene varied with its exposure concentration. As reported by ACGIH (1996) and CCINFO (1998), eye, nose, and throat irritation were observed in 200 parts per million (ppm) xylene concentration. Slight lightheadedness, nausea and vomiting, and death within 6 h are the effects of 230, 700, and 10,000 ppm, respectively. Table 1 illustrates the xylene health effects in (erms of short-term and long-term exposure, This table has been constructed using data published in the literature (ATSDR, 1993; Hallenbeck, and Cunningham, 1985; CCINFO, 1998; Riihimaki and Savolainen, 1980; Bratveit et al., 2007; Carpenter et al., 1975). To protect people from the potential harmful health effects of xylene, the Environmental Protection Agency (EPA) TABLE 1 Long Term and Short Term Exposure to Xylene Long Term Short Term Central nervous system (CNS) dysfunction, excitation, Increase in liver enzymes and depression Inflammation of skin including dryness and cracking Irritation of nose, throat, and eyes Reversible kidney Headache Liver damage Nausea Anorexia Vomiting chension Dizziness wrtow hyperplasia Fatigue Dermatitis Instability Drowsiness Abdominal pain Bye injury Loss of appetite Flatulence Reduced coordination Gastrointestinal pain Loss of consciousness ‘Memory impairment Tissues destruction Hepatic damage Amnesia Mucosal hemorrhage Brain hemorhage Nausea Cardiac stress Red and white blood cell abnormalities Dermatitis ‘Abnormal heartbeat (in laboratory workers) Liver and kidney damage Cholinesterase depression Respiratory difficulties Epilepsy Tremor Faty liver Hyperplasia Mutagenesis Prenatal damage Reproductive systems effects Death in humans due to respiratory failureDownloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 CLEAN UP OF ASPHALTENE DEPOSITS IN OIL WELLS 27 regulates xylene in the environment. The EPA estimates that, for an adult of average weight who drinks two liters of water each day for a lifetime (70 years), exposure to 7 ppm xylene in drinking water is unlikely to result in harmful noncancerous health effects. Exposure to 40 ppm xylene in water for 1 or 10 days is unlikely to present a health risk to a small child. The EPA has set a legally enforceable maximum level of 10 ppm of xylene in water that is delivered to any user of a public water system. Occupational Safety and Health Administration (OSHA) regulates levels of xylene in the workplace. The maximum allowable amount of xylene in workroom air during an 8h workday in a 40h workweek is 100 ppm (ATSDR, 2007). OSHA has been installed to protect workers from solvent exposure, Indeed, OSHA has implemented strict regulations, called permissible exposure limits (PEL), for chemical concentrations to which one may be exposed without detrimental health effects. As a result of the impacts of these regulations, many methods for solvent pollution prevention have been developed (Englehardt, 1993; Venkataramani et al., 1992; Haggin, 1995; Sheldon, 1994; Lipton, 1992; Abmad, 1997; Dienemann and Bacher, 1994). Curtis (2003) introduced environmental friendly terpene-based solvents that contain much-improved HSE characteristics. As pointed out by Lightford et al. (2006), a new emulsified solvent system (ESS) achieved enhanced HSE characteristics, as well as excellent asphaltene-solvency power and the additional benefit of leaving the formation strongly water-wet. Unfortunately, there are no national standards, especially for air quality in Iran and so the levels of xylene reported by Halek et al, (2004) shows that the amount of xylene may be some 30 times the allowed limit. As indicated by recent research (Bahrami et al. 2008) high xylene levels are emitted in petrol stations at Iran. Zadeh et al. (2010) demonstrated that the concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX) are extremely high in Tehran rainwater samples (mean concentration of BTEX was between 87 and 188 j1g/L). It was concluded that contaminated rainwater can be the major source of hydrocarbon pollution in ‘Tehran soil and groundwater. 3, TECHNICAL DRAWBACKS OF XYLENE IN OIL WELL STIMULATION Xylene is widely used as stimulation fuid in Iranian oil and gas fields. The amount of xylene usage in one of the largest Iranian oil and gas producers in 1 year reached to 9,200 barrels (Shadizadeh and Zoveidavianpoor, 2008). Figure 2 shows an example of xylene usage for 11 wells in duration of 7 years in a reservoir located in the south of Iran. Typically, producers perform systematic removal treatments to overcome the effects of asphaltene deposits. Historically, xylene has been used to remove these organic deposits; however, xylene does not change the wettability of the rock surface, resulting in treatment effectiveness that is often short-lived. As asserted by Trbovich and King, (1991), single solvent treatments of xylene were successful in most cases in restoring production, but failed to achieve a long-lasting productivity increase. In addition, solvents such as xylene did not completely dissolve the asphalt deposits (Ransley, 1984; Coppel, 1972) or completely extract asphaltenes fixed on rock surfaces (Dubey and Waxman, 1991). Conventional hydrocarbon solvents used for asphaltene treatment and removal leaves the formation and tubing in an oil wet condition, such that re-deposition of asphaltene may be accelerated and thereby increase the rate of production decline. Recent researches found that xylene is not a long-term solution to asphaltene precipitation and will fasten its deposition in the wellbore. Consequently, after injection of xylene for several times, matrix acidizing cannot remove the skin that formed around the wellbore. This article docs not present detailed data and discussion on matrix acidizing failure in Iran’s carbonate fields because that topic is thoroughly covered elsewhere (Zoveidavianpoor et al., 2010). Figure 3 is an example for this failure and ineffective usage of xylene in K reservoir. An onshore oil reservoir, named K, in Iran produces from two limestone reservoir's X and Y, both containing asphaltic crudes. The majority of theDownloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 28° M. ZOVEIDAVIANPOOR ET AL, 800 00 400 200 oe eee 2001 4997 19992000 2002 200320042008 Xylene usage, Barrel FIGURE 2 Xylene usage in 11 wells in duration of 7 years in Iran. (Source: Shadizadeh and Zoveidavianpoor, 2008.) wells producing from reservoir X suffer from severe hard asphaltene deposition in the production system causing increased pressure loss across the string resulting in increased loss of production. In order to mitigate asphaltene deposition, xylene is used for the removal operation, but it was not successful. Figure 3 clearly shows that the majority of production declines in K reservoir were resulted from asphaltene precipitation. In addition to high operational cost of xylene usage, Daly Prato, bed FIGURE 3 Daily oil production of a new developed well in south of Iran, suffering from asphaltene deposition (color figure available online)Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 CLEAN UP OF ASPHALTENE DEPOSITS IN OIL WELLS 29 downtimes and production losses of the wells may be arising from ineffective application of xylene and improper attention to find an alternative solvent. Indeed, asphaltene is considered to be the main cause of formation damage in southern Iranian reservoirs. It must be noted that asphaltene has a wide variety of potential structures and varies from reservoir to reservoir. The actual structure apparently depends on the source of the oil and the asphaltic material. 4. DISCUSSION Acute (short-term) and chronic (long-term) exposures to xylenes have been illustrated in Table 1 Because there was no study performed in an upstream petroleum industry about the HSE impacts of xylene, some investigations in other industries had been performed (Halek et al., 2004; Bahrami et al,, 2008; Zadeh et al., 2010). Aside from the brief discussion and various associated problems of the current stimulation method (matrix acidizing), the main cause of formation damage in the current stimulation operation is asphaltene precipitation. It is obvious that xylene usage for removing asphaltene precipitation is not considered as a cure for pain, perhaps it is a pain for pain. Asphaltene plugs have caused enormous downtimes for oil production, put at risk oil economics, and increased the cost of production of many oil fields in Iran. Xylene is widely used as stimulation fluid in Iranian oil and gas fields. The amount of xylene usage in one of the Iranian oil and gas producers in 1 year reached to 9,200 barrels (Shadizadeh and Zoveidavianpoor, 2008). As an example, Figure 2 shows an increased trend of xylene usage in 11 oil wells for a duration of 7 years. Unfortunately, lack of rules and regulation about xylene utilization in Iran had a negative impact on technical and HSE, issues. Continuing tacking advantage of xylene as a main stimulation fluid for asphaltene clean up had caused the upstream industry not to investigate for environmental friendly and technical improvement of stimulation fluid, Additionally, there is no a single study about HSE effects of xylene in upstream oil industry. One of the major drawbacks of solvents, such as toluene and xylene, is that they will usually dissolve only 50% of a typical downhole sample. In addition, the deposits in the wellbore are typically not only asphaltene and can comprise other organic or inorganic deposits in addition to water (Lightford et al., 2006). Experiments have shown that clean up with pure toluene removes most of the asphaltene fraction, but the surface will still be covered with asphaltenes (Speight and Moschopedis, 1981). The nature of the remaining asphaltenes is likely to be the most polar and highest molecular weight fraction. As a consequence, the core surface wil still be intermediate to oil-wet. Because an asphaltene-covered surface is more prone to redeposit of asphaltenes (Irbovich and King, 1991), cleanup should be as efficient as possible. As concluded by Zoveidavianpoor et al, (2010, 2011), reducing the pressure drop, or drawdown, via effective stimulation is considered the main way to delay asphaltene deposition. As mentioned previously, pressure drop is one of the key causes of asphaltene deposition; the damaged zone in- creases with the current operation, so the pressure drop across skin Ap,i Will continue to increase with the conventional stimulation procedures. A detailed discussion of pressure maintenance in the production system can be found by Shadizadeh and Zoveidavianpoor (2009). The impact of regulations on solvent’s usage has caused a reduction of their uses, and many methods for solvent pollution prevention have been developed. Solvent replacement techniques have also come to the forefront as many solvents are banned or discouraged from industrial uses. Unfortunately, due to lack of environmental regulations in Iranian oil/gas industry for use of solvents, xylene is widely used as a well stimulation fluid. The amount of xylene usage in one of the largest Iranian oil and gas producers is around to 9,200 barrels/year per 1,000 wells stimulation jobs.Downloaded by [Universiti Teknologi Malaysia] at 19:13 30 November 2012 30M. ZOVEIDAVIANPOOR ET AL, Xylene impacts, which are discussed in this article, can be an effective awareness to upstream petroleum industry. The authors tried to present it in ways that strengthen the desire to seck deeper understanding of its impacts. By paying more attention to the different aspects of xylene usage in stimulation jobs, improving the quality and efficiency of solvents to be used in asphaltene removal operations can better be triggered. Furthermore, such insights will improve engineering and environmental protection. 5. 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